Film production method

ABSTRACT

A method of producing a film having excellent external quantum efficiency when used in a light emitting layer of a light emitting device is provided. A method of film production includes preparing an ink containing a specific metal complex, storing the ink for 3 days or more under light shielding, and forming a film by using the stored ink. The total content of metal complexes having a molecular weight larger by 16, 32 or 48 than that of the specific metal complex according to an area percentage value determined by liquid chromatography is 0.6 or less when the content of the specific metal complex is taken as 100.

TECHNICAL FIELD

The present invention relates to a film production method using an inkcomprising a metal complex and an organic solvent, and the like.

BACKGROUND ART

Light emitting devices such as an organic electroluminescent device canbe suitably used in applications of display and illumination because ofproperties such as high external quantum efficiency and low voltagedriving. As the light emitting material used for a light emitting layerof a light emitting device, for example, a phosphorescent metal complexwhich shows light emission from the triplet excited state is known.

As a method of forming a film to be a light emitting layer of a lightemitting device, an application method using a solvent is advantageousfrom the standpoint of simplification of a production process for alarge area device and reduction of the production cost. On the otherhand, it is known that if oxygen is present in an ink comprising aphosphorescent metal complex used in an application method, the lightemitting property is deteriorated (Patent Document 1).

PRIOR ART DOCUMENT

[Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No.2002-170677

SUMMARY OF THE INVENTION Problem to be Solved by the Invention

Depending on the phosphorescent metal complex, however, even if oxygencontained in the ink is only reduced by an deoxygenation treatment, theexternal quantum efficiency of a light emitting device comprising a film(light emitting layer) obtained by using the ink is not sufficient.

Then, the present invention is intended to provide a method of producinga film excellent in the external quantum efficiency when used in a lightemitting layer of a light emitting device, and the like.

Means for Solving the Problem

The present invention provides the following [1] to [15].

[1] A film production method comprising

an ink preparation step of preparing an ink comprising a metal complexrepresented by the formula (1-A) or the formula (1-B), and an organicsolvent,

an ink storage step of storing the ink prepared in the ink preparationstep for 3 days or more under light shielding, and

a film formation step of forming a film by an application method usingthe ink stored in the ink storage step and in which the total content ofmetal complexes having a molecular weight larger by 16, 32 or 48 thanthat of the metal complex represented by the formula (1-A) or theformula (1-B) according to the area percentage value determined byliquid chromatography is 0.6 or less when the content of the metalcomplex represented by the formula (1-A) or the formula (1-B) accordingto the area percentage value determined by liquid chromatography istaken as 100:

[wherein,

M represents an iridium atom or a platinum atom.

n¹ represents an integer of 1 or more, n² represents an integer of 0 ormore, and n¹+n² is 2 or 3. n¹+n² is 3 when M is an iridium atom, whilen¹+n² is 2 when M is a platinum atom.

E¹ represents a carbon atom or a nitrogen atom. When a plurality of E¹are present, they may be the same or different.

E^(11A), E^(12A), E^(13A), E^(21A), E^(22a), E^(23A) and E^(24A) eachindependently represent a nitrogen atom or a carbon atom. When aplurality of E^(11A), E^(12A), E^(13a), E^(21a), E^(22a), E^(23A) andE^(24A) are present, they may be the same or different at eachoccurrence. When E^(11A) is a nitrogen atom, R^(11A) may be eitherpresent or not present. When E^(12A) is a nitrogen atom, R^(12A) may beeither present or not present. When E^(13A) is a nitrogen atom, R^(13A)may be either present or not present. When E^(21A) is a nitrogen atom,R^(21A) is not present. When E^(22A) is a nitrogen atom, R^(22A) is notpresent. When E^(23A) is a nitrogen atom, R^(23A) is not present. WhenE^(24A) is a nitrogen atom, R^(24A) is not present.

R^(11A), R^(12a), R^(13a), R^(21a), R^(22a), R^(23A) and R^(24A) eachindependently represent a hydrogen atom, an alkyl group, a cycloalkylgroup, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxygroup, a monovalent heterocyclic group, a halogen atom or a substitutedamino group, or R^(11A) and R^(12A), R^(12A) and R^(13A), R^(11A) andR^(21A), R^(21A) and R^(22A), R^(22A) and R^(23A), and R^(23A) andR^(24A) each are combined together to form an aromatic ring togetherwith the atoms to which they are attached. The group represented byR^(11A), R^(12A), R^(13A), R^(21A), R^(22A), R^(23A) or R^(24A)optionally has a substituent. When a plurality of R^(11A), R^(12A),R^(13A), R^(21A), R^(22A), R^(23A) and R^(24A) are present, they may bethe same or different at each occurrence. R^(11A) and R^(12A), R^(12A)and R^(13A), R^(11A) and R^(21A), R^(21A) and R^(22A), R^(22A) andR^(23A), and R^(23A) and R^(24A) each may be combined together to form aring together with the atoms to which they are attached.

The ring R^(1A) represents a diazole ring or a triazole ring constitutedof a nitrogen atom, E², E^(11A), E^(12A) and E^(13A).

The ring R^(2A) represents a benzene ring, a pyridine ring or a diazinering constituted of two carbon atoms, E^(21A), E^(22A), E^(23A) andE^(24A).

A¹-G¹-A² represents an anionic bidentate ligand, A¹ and A² eachindependently represent a carbon atom, an oxygen atom or a nitrogenatom, and these atoms each may be an atom constituting a ring. G¹represents a single bond or an atomic group constituting the bidentateligand together with A¹ and A². When a plurality of A¹-G¹-A² arepresent, they may be the same or different.]

[wherein,

M, n¹, n² and A¹-G¹-A² represent the same meaning as described above.

E^(11B), E^(12B), E^(13B), E^(14B), E^(21B), E^(22B), E^(23B) andE^(24B) each independently represent a nitrogen atom or a carbon atom.When a plurality of E^(11B), E^(12B), E^(13B), E^(14B), E^(21B),E^(22B), E^(23B) and E^(24B) are present, they may be the same ordifferent at each occurrence. When E^(11B) is a nitrogen atom, R^(11B)is not present. When E^(12B) is a nitrogen atom, R^(12B) is not present.When E^(13B) is a nitrogen atom, R^(13B) is not present. When E^(14B) isa nitrogen atom, R^(14B) is not present. When E^(21B) is a nitrogenatom, R^(21B) is not present. When E^(22B) is a nitrogen atom, R^(22B)is not present. When E^(23B) is a nitrogen atom, R^(23B) is not present.When E^(24B) is a nitrogen atom, R^(24B) is not present.

R^(11B), R^(12B), R^(13B), R^(14B), R^(21B), R^(22B), R^(23B) andR^(24B) each independently represent a hydrogen atom, an alkyl group, acycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group,an aryloxy group, a monovalent heterocyclic group, a halogen atom or asubstituted amino group, or R^(11B) and R^(12B), R^(12B) and R^(13B),R^(13B) and R^(14B), R^(11B) and R^(21B), R^(21B) and R^(22B), R^(22B)and R^(23B), and R^(23B) and R^(24B) each are combined together to forman aromatic ring together with the atoms to which they are attached. Thegroup represented by R^(11B), R^(12B), R^(13B), R^(14B), R^(21B),R^(22B), R^(23B) or R^(24B) optionally has a substituent. When aplurality of R^(11B), R^(12B), R^(13B), R^(14B), R^(21B), R^(22B),R^(23B) and R^(24B) are present, they may be the same or different ateach occurrence. R^(11B) and R^(12B), R^(12B) and R^(13B), R^(13B) andR^(14B), R^(11B) and R^(21B), R^(21B) and R^(22B), R^(22B) and R^(23B),and R^(23B) and R^(24B) each may be combined together to form a ringtogether with the atoms to which they are attached.

The ring R^(1B) represents a pyridine ring or a diazine ring constitutedof a nitrogen atom, a carbon atom, E^(11B), E^(12B), E^(13B) andE^(14B).

The ring R^(2B) represents a benzene ring, a pyridine ring or a diazinering constituted of two carbon atoms, E^(21B), E^(22B), E^(23B) andE^(24B).].

[2] The film production method according to [1], wherein the ink storagestep is performed under the condition of 0° C. to 50° C.

[3] The film production method according to [1] or [2], wherein the inkstorage step is performed under an inert gas atmosphere.

[4] The film production method according to any one of [1] to [3],wherein the metal complex (1-A) is a metal complex represented by theformula (1-A1), a metal complex represented by the formula (1-A2), ametal complex represented by the formula (1-A3) or a metal complexrepresented by the formula (1-A4):

[wherein,

M, n², n², R^(11A), R^(12A), R^(13A), R^(21A), R^(22A), R^(23A), R^(24A)and A¹-G¹-A² represent the same meaning as described above.].

[5] The film production method according to any one of [1] to [3],wherein the metal complex (1-B) is a metal complex represented by theformula (1-B1), a metal complex represented by the formula (1-B2) or ametal complex represented by the formula (1-B3):

[wherein,

M, n¹, n², R^(11B), R^(12B), R^(13B), R^(14B), R^(21B), R^(22B),R^(23B), R^(24B) and A¹-G¹-A² represent the same meaning as describedabove.

R^(15B), R^(16B), R^(17B) and R^(18B) each independently represent ahydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, acycloalkoxy group, an aryl group, an aryloxy group, a monovalentheterocyclic group, a halogen atom or a substituted amino group, andthese groups each optionally have a substituent. When a plurality ofR^(15B), R^(16B), R^(17B) and R^(18B) are present, they may be the sameor different at each occurrence.].

[6] The film production method according to any one of [1] to [5],wherein the ink further comprises a compound represented by the formula(H-1):

[wherein,

Ar^(H1) and Ar^(H2) each independently represent an aryl group or amonovalent heterocyclic group, and these groups each optionally have asubstituent.

n^(H1) and n^(H2) each independently represent 0 or 1. When a pluralityof n^(H1) are present, they may be the same or different. The pluralityof n^(H2) may be the same or different.

n^(H3) represents an integer of 0 to 10.

L^(H1) represents an arylene group, a divalent heterocyclic group or agroup represented by —[C(R^(H11))₂] n^(H11)-, and these groups eachoptionally have a substituent. When a plurality of L^(H1) are present,they may be the same or different.

n^(H11) represents an integer of 1 to 10. R^(H11) represents a hydrogenatom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxygroup, an aryl group or a monovalent heterocyclic group, and thesegroups each optionally have a substituent. The plurality of R^(H11) maybe the same or different and may be combined together to form a ringtogether with the carbon atoms to which they are attached.

L^(H2) represents a group represented by —N(-L^(H21)-R^(H21))—. When aplurality of L^(H2) are present, they may be the same or different.

L^(H21) represents a single bond, an arylene group or a divalentheterocyclic group, and these groups each optionally have a substituent.R^(H21) represents a hydrogen atom, an alkyl group, a cycloalkyl group,an aryl group or a monovalent heterocyclic group, and these groups eachoptionally have a substituent.].

[7] The film production method according to any one of [1] to [5],wherein the ink further comprises a polymer compound comprising aconstitutional unit represented by the formula (Y):

[Chemical Formula 6]

Ar^(Y1)  (Y)

[wherein, Ar^(Y1) represents an arylene group, a divalent heterocyclicgroup or a divalent group in which at least one arylene group and atleast one divalent heterocyclic group are bonded directly to each other,and these groups each optionally have a substituent.].

[8] An ink storage method comprising

an ink preparation step of preparing an ink comprising a metal complexrepresented by the above-described formula (1-A) or the above-describedformula (1-B), and an organic solvent, and

a storage step of storing the ink prepared in the above-described inkpreparation step for 3 days or more,

wherein the content of the metal complex represented by theabove-described formula (1-A) or formula (1-B) in the ink immediatelyafter preparation of the ink preparation step is defined as Cb[M], thetotal content of metal complexes having a molecular weight larger by 16,32 or 48 than that of the metal complex represented by theabove-described formula (1-A) or formula (1-B) in the ink immediatelyafter the preparation is defined as Cb[M+16n], the content of the metalcomplex represented by the above-described formula (1-A) or formula(1-B) in the ink immediately after storage of the storage step isdefined as Ca[M], and the total content of metal complexes having amolecular weight larger by 16, 32 or 48 than that of the metal complexrepresented by the above-described formula (1-A) or formula (1-B) in theink immediately after the storage is defined as Ca[M+16n], satisfyingthe formulae (1) and (2):

0.1≤(Ca[M+16n]/Ca[M])/(Cb[M+16n]/Cb[M])≤20  (1)

0<Ca[M+16n]/Ca[M]≤0.006  (2).

[9] The ink storage method according to [8], wherein the storage step isperformed under light shielding.

[10] The ink storage method according to [8] or [9], wherein the storagestep is performed under the condition of 0° C. to 50° C.

[11] The ink storage method according to any one of [8] to [10], whereinthe storage step is performed under an inert gas atmosphere.

[12] The ink storage method according to any one of [8] to [11], whereinthe above-described metal complex (1-A) is a metal complex representedby the above-described formula (1-A1), a metal complex represented bythe above-described formula (1-A2), a metal complex represented by theabove-described formula (1-A3) or a metal complex represented by theabove-described formula (1-A4).

[13] The ink storage method according to any one of [8] to [12], whereinthe above-described metal complex (1-B) is a metal complex representedby the above-described formula (1-B1), a metal complex represented bythe above-described formula (1-B2) or a metal complex represented by theabove-described formula (1-B3).

[14] The ink storage method according to any one of [8] to [13], whereinthe ink further comprises a compound represented by the above-describedformula (H-1).

[15] The ink storage method according to any one of [8] to [13], whereinthe ink further comprises a polymer compound comprising a constitutionalunit represented by the above-described formula (Y).

Effect of the Invention

According to the film production method of the present invention or thelike, a film excellent in the external quantum efficiency when used fora light emitting layer of a light emitting device is obtained.

MODES FOR CARRYING OUT THE INVENTION

Suitable embodiments of the present invention will be illustrated indetail below.

<Explanation of Common Term>

Terms commonly used in the present specification have the followingmeanings unless otherwise stated.

Me represents a methyl group, Et represents an ethyl group, Burepresents a butyl group, i-Pr represents an isopropyl group, and t-Burepresents a tert-butyl group.

A hydrogen atom may be a heavy hydrogen atom or a light hydrogen atom.

A solid line representing a bond to a central metal in a formularepresenting a metal complex denotes a covalent bond or a coordinatebond.

“Polymer compound” denotes a polymer having molecular weightdistribution and having a polystyrene-equivalent number averagemolecular weight of 1*10³ to 1*10⁸.

A polymer compound may be any of a block copolymer, a random copolymer,an alternating copolymer and a graft copolymer, and may also be anotherembodiment.

An end group of a polymer compound is preferably a stable group becauseif a polymerization active group remains intact at the end, when thepolymer compound is used for fabrication of a light emitting device, thelight emitting property or luminance life possibly becomes lower. Thisend group is preferably a group having a conjugated bond to the mainchain, and includes, for example, groups bonding to an aryl group or amonovalent heterocyclic group via a carbon-carbon bond.

“Low molecular weight compound” denotes a compound having no molecularweight distribution and having a molecular weight of 1×10⁴ or less.

“Constitutional unit” denotes a unit structure found once or more in apolymer compound.

“Alkyl group” may be any of linear or branched. The number of carbonatoms of the linear alkyl group is, not including the number of carbonatoms of a substituent, usually 1 to 50, preferably 3 to 30, morepreferably 4 to 20. The number of carbon atoms of the branched alkylgroups is, not including the number of carbon atoms of a substituent,usually 3 to 50, preferably 3 to 30, more preferably 4 to 20.

The alkyl group optionally has a substituent, and examples thereofinclude a methyl group, an ethyl group, a propyl group, an isopropylgroup, a butyl group, an isobutyl group, a tert-butyl group, a pentylgroup, an isoamyl group, a 2-ethylbutyl group, a hexyl group, a heptylgroup, an octyl group, a 2-ethylhexyl group, a 3-propylheptyl group, adecyl group, a 3,7-dimethyloctyl group, a 2-ethyloctyl group, a2-hexyldecyl group and a dodecyl group, and groups obtained bysubstituting a hydrogen atom in these groups with a cycloalkyl group, analkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom or thelike, and the alkyl group having a substituent includes atrifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group,a perfluorohexyl group, a perfluorooctyl group, a 3-phenylpropyl group,a 3-(4-methylphenyl)propyl group, a 3-(3,5-di-hexylphenyl) propyl groupand a 6-ethyloxyhexyl group.

The number of carbon atoms of “Cycloalkyl group” is, not including thenumber of carbon atoms of a substituent, usually 3 to 50, preferably 3to 30, more preferably 4 to 20.

The cycloalkyl group optionally has a substituent, and examples thereofinclude a cyclohexyl group, a cyclohexylmethyl group and acyclohexylethyl group.

“Aryl group” denotes an atomic group remaining after removing from anaromatic hydrocarbon one hydrogen atom linked directly to a carbon atomconstituting the ring. The number of carbon atoms of the aryl group is,not including the number of carbon atoms of a substituent, usually 6 to60, preferably 6 to 20, more preferably 6 to 10.

The aryl group optionally has a substituent, and examples thereofinclude a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a1-pyrenyl group, a 2-pyrenyl group, a 4-pyrenyl group, a 2-fluorenylgroup, a 3-fluorenyl group, a 4-fluorenyl group, a 2-phenylphenyl group,a 3-phenylphenyl group, a 4-phenylphenyl group, and groups obtained bysubstituting a hydrogen atom in these groups with an alkyl group, acycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, afluorine atom or the like.

“Alkoxy group” may be any of linear or branched. The number of carbonatoms of the linear alkoxy group is, not including the number of carbonatoms of a substituent, usually 1 to 40, preferably 4 to 10. The numberof carbon atoms of the branched alkoxy group is, not including thenumber of carbon atoms of a substituent, usually 3 to 40, preferably 4to 10.

The alkoxy group optionally has a substituent, and examples thereofinclude a methoxy group, an ethoxy group, a propyloxy group, anisopropyloxy group, a butyloxy group, an isobutyloxy group, atert-butyloxy group, a pentyloxy group, a hexyloxy group, a heptyloxygroup, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, adecyloxy group, a 3,7-dimethyloctyloxy group and a lauryloxy group, andgroups obtained by substituting a hydrogen atom in these groups with acycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, afluorine atom or the like.

The number of carbon atoms of “Cycloalkoxy group” is, not including thenumber of carbon atoms of a substituent, usually 3 to 40, preferably 4to 10.

The cycloalkoxy group optionally has a substituent, and examples thereofinclude a cyclohexyloxy group.

The number of carbon atoms of “Aryloxy group” is, not including thenumber of carbon atoms of a substituent, usually 6 to 60, preferably 7to 48.

The aryloxy group optionally has a substituent, and examples thereofinclude a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a1-anthracenyloxy group, a 9-anthracenyloxy group, a 1-pyrenyloxy group,and groups obtained by substituting a hydrogen atom in these groups withan alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxygroup, a fluorine atom or the like.

“p-Valent heterocyclic group” (p represents an integer of 1 or more)denotes an atomic group remaining after removing from a heterocycliccompound p hydrogen atoms among hydrogen atoms directly linked to acarbon atom or a hetero atom constituting the ring. Of p-valentheterocyclic groups, “p-valent aromatic heterocyclic groups” as anatomic group remaining after removing from an aromatic heterocycliccompound p hydrogen atoms among hydrogen atoms directly linked to acarbon atom or a hetero atom constituting the ring are preferable.

“Aromatic heterocyclic compound” denotes a compound in which theheterocyclic ring itself shows aromaticity such as oxadiazole,thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan,pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline,isoquinoline, carbazole, dibenzosilole and dibenzophosphole, and acompound in which an aromatic ring is condensed to the heterocyclic ringeven if the heterocyclic ring itself shows no aromaticity such asphenoxazine, phenothiazine, dibenzoborole, dibenzosilole and benzopyran.

The number of carbon atoms of the monovalent heterocyclic group is, notincluding the number of carbon atoms of a substituent, usually 2 to 60,preferably 4 to 20.

The monovalent heterocyclic group optionally has a substituent, andexamples thereof include a thienyl group, a pyrrolyl group, a furylgroup, a pyridyl group, a piperidyl group, a quinolinyl group, anisoquinolinyl group, a pyrimidinyl group, a triazinyl group, and groupsobtained by substituting a hydrogen atom in these groups with an alkylgroup, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or thelike.

“Halogen atom” denotes a fluorine atom, a chlorine atom, a bromine atomor an iodine atom.

“Amino group” optionally has a substituent, and a substituted aminogroup is preferable. The substituent which an amino group has ispreferably an alkyl group, a cycloalkyl group, an aryl group or amonovalent heterocyclic group.

The substituted amino group includes, for example, a dialkylamino group,a dicycloalkylamino group and a diarylamino group.

The amino group includes, for example, a dimethylamino group, adiethylamino group, a diphenylamino group, a bis(4-methylphenyl)aminogroup, a bis(4-tert-butylphenyl)amino group and abis(3,5-di-tert-butylphenyl)amino group.

“Alkenyl group” may be any of linear or branched. The number of carbonatoms of the linear alkenyl group, not including the number of carbonatoms of the substituent, is usually 2 to 30, preferably 3 to 20. Thenumber of carbon atoms of the branched alkenyl group, not including thenumber of carbon atoms of the substituent, is usually 3 to 30,preferably 4 to 20.

The number of carbon atoms of “Cycloalkenyl group”, not including thenumber of carbon atoms of the substituent, is usually 3 to 30,preferably 4 to 20.

The alkenyl group and cycloalkenyl group each optionally have asubstituent, and examples thereof include a vinyl group, a 1-propenylgroup, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group, a 5-hexenylgroup, a 7-octenyl group, and these groups having a substituent.

“Alkynyl group” may be any of linear or branched. The number of carbonatoms of the alkynyl group, not including the number of carbon atoms ofthe substituent, is usually 2 to 20, preferably 3 to 20. The number ofcarbon atoms of the branched alkynyl group, not including the number ofcarbon atoms of the substituent, is usually 4 to 30, preferably 4 to 20.

The number of carbon atoms of “Cycloalkynyl group”, not including thenumber of carbon atoms of the substituent, is usually 4 to 30,preferably 4 to 20.

The alkynyl group and cycloalkynyl group each optionally have asubstituent, and examples thereof include an ethynyl group, a 1-propynylgroup, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a3-pentynyl group, a 4-pentynyl group, a 1-hexynyl group, a 5-hexynylgroup, and these groups having a substituent.

“Arylene group” denotes an atomic group remaining after removing from anaromatic hydrocarbon two hydrogen atoms linked directly to carbon atomsconstituting the ring. The number of carbon atoms of the arylene groupis, not including the number of carbon atoms of a substituent, usually 6to 60, preferably 6 to 30, more preferably 6 to 18.

The arylene group optionally has a substituent, and examples thereofinclude a phenylene group, a naphthalenediyl group, an anthracenediylgroup, a phenanthrenediyl group, a dihydrophenanthrenediyl group, anaphthalenediyl group, a fluorenediyl group, a pyrenediyl group, aperylenediol group, a chrysenediol group, and these groups having asubstituent, preferably, groups represented by the formulae (A-1) to(A-20). The arylene group includes groups obtained by linking aplurality of these groups.

[wherein, R and R^(a) each independently represent a hydrogen atom, analkyl group, a cycloalkyl group, an aryl group or a monovalentheterocyclic group. The plurality of R and R³ each may be the same ordifferent, and groups R^(a) may be combined together to form a ringtogether with the atoms to which they are attached.]

The number of carbon atoms of the divalent heterocyclic group is, notincluding the number of carbon atoms of a substituent, usually 2 to 60,preferably 3 to 20, more preferably 4 to 15.

The divalent heterocyclic group optionally has a substituent, andexamples thereof include divalent groups obtained by removing frompyridine, diazabenzene, triazine, azanaphthalene, diazanaphthalene,carbazole, dibenzofuran, dibenzothiophene, dibenzosilole, phenoxazine,phenothiazine, acridine, dihydroacridine, furan, thiophene, azole,diazole and triazole two hydrogen atoms among hydrogen atoms linkingdirectly to a carbon atom or a hetero atom constituting the ring,preferably groups represented by the formulae (AA-1) to (AA-34).

The divalent heterocyclic group includes groups obtained by linking aplurality of these groups.

“Crosslinkable group” is a group capable of forming a new bond by beingsubjected to a heating treatment, an ultraviolet irradiation treatment,a radical reaction and the like, and the crosslinkable group ispreferably any one of groups represented by the formulae (B-1) to(B-17). These groups each optionally have a substituent.

“Substituent” represents a halogen atom, a cyano group, an alkyl group,a cycloalkyl group, an aryl group, a monovalent heterocyclic group, analkoxy group, a cycloalkoxy group, an aryloxy group, an amino group, asubstituted amino group, an alkenyl group, a cycloalkenyl group, analkynyl group or a cycloalkynyl group. The substituent may be acrosslinkable group.

“Dendron” is a group having a regular dendritic branched structurehaving a branching point at an atom or ring (that is, a dendrimerstructure). A compound having a dendron (hereinafter, referred to as“dendrimer”.) includes, for example, structures described in literaturessuch as International Publication WO 02/067343, JP-A No. 2003-231692,International Publication WO 2003/079736, and International PublicationWO 2006/097717.

The dendron is preferably a group represented by the formula (D-A) or(D-B).

[wherein,

m^(DA1), m^(DA2) and m^(DA3) each independently represent an integer of0 or more.

G^(DA) represents a nitrogen atom, an aromatic hydrocarbon group or aheterocyclic group, and these groups each optionally have a substituent.

Ar^(DA1), Ar^(DA2) and Ar^(DA3) each independently represent an arylenegroup or a divalent heterocyclic group, and these groups each optionallyhave a substituent. When a plurality of Ar^(DA1), Ar^(DA2) and Ar^(DA3)are present, they may be the same or different at each occurrence.

T^(DA) represents an aryl group or a monovalent heterocyclic group, andthese groups each optionally have a substituent. The plurality of T^(DA)may be the same or different.]

[wherein,

m^(DA1), m^(DA2), m^(DA3), m^(DA4), m^(DA5), m^(DA6) and m^(DA7) eachindependently represent an integer of 0 or more.

G^(DA) represents a nitrogen atom, an aromatic hydrocarbon group or aheterocyclic group, and these groups each optionally have a substituent.The plurality of G^(DA) may be the same or different.

Ar^(DA1), Ar^(DA2), Ar^(DA3), Ar^(DA4), Ar^(DA5), Ar^(DA6) and Ar^(DA7)each independently represent an arylene group or a divalent heterocyclicgroup, and these groups each optionally have a substituent. When aplurality of Ar^(DA1), Ar^(DA2), Ar^(DA3), Ar^(DA4), Ar^(DA5), Ar^(DA6)and Ar^(DA7) are present, they may be the same or different at eachoccurrence.

T^(DA) represents an aryl group or a monovalent heterocyclic group, andthese groups each optionally have a substituent. The plurality of T^(DA)may be the same or different.]

m^(DA1), m^(DA2), m^(DA3), m^(DA4), m^(DA5), m^(DA6) and m^(DA7) areusually an integer of 10 or less, preferably an integer of 5 or less,more preferably 0 or 1. Itis preferable that m^(DA1), m^(DA2), m^(DA3),m^(DA4), m^(DA5), m^(DA6) and m^(DA7) are the same integer.

G^(DA) is preferably a group represented by the formula (GDA-11) to(GDA-15), and these groups each optionally have a substituent.

[wherein,

* represents a linkage to Ar^(DA1) in the formula (D-A), Ar^(DA1) in theformula (D-B), Ar^(DA2) in the formula (D-B) or Ar^(DA3) in the formula(D-B).

** represents a linkage to Ar^(DA2) in the formula (D-A), Ar^(DA2) inthe formula (D-B), Ar^(DA4) in the formula (D-B) or Ar^(DA6) in theformula (D-B).

*** represents a linkage to Ar^(DA3) in the formula (D-A), A³ in theformula (D-B), Ar^(DA5) in the formula (D-B) or Ar^(DA7) in the formula(D-B).

R^(DA) represents a hydrogen atom, an alkyl group, a cycloalkyl group,an alkoxy group, a cycloalkoxy group, an aryl group or a monovalentheterocyclic group, and these groups each optionally have a substituent.When a plurality of R^(DA) are present, they may be the same ordifferent.]

R^(DA) is preferably a hydrogen atom, an alkyl group, a cycloalkylgroup, an alkoxy group or a cycloalkoxy group, more preferably ahydrogen atom, an alkyl group or cycloalkyl group, and these groups eachoptionally have a substituent.

It is preferable that Ar^(DA1), Ar^(DA2), Ar^(DA3), Ar^(DA4), Ar^(DA5),Ar^(DA6) and Ar^(DA7) are groups represented by the formulae (ArDA-1) to(ArDA-3).

[wherein,

R^(DA) represents the same meaning as described above.

R^(DB) represents a hydrogen atom, an alkyl group, a cycloalkyl group,an aryl group or a monovalent heterocyclic group, and these groups eachoptionally have a substituent. When a plurality of R^(DB) are present,they may be the same or different at each occurrence.]

R^(DB) is preferably an alkyl group, a cycloalkyl group, an aryl groupor a monovalent heterocyclic group, more preferably an aryl group or amonovalent heterocyclic group, further preferably an aryl group.

T^(DA) is preferably groups represented by the formulae (TDA-1) to(TDA-3).

[wherein, R^(DA) and R^(DB) represent the same meaning described above.]

The group represented by the formula (D-A) is preferably a grouprepresented by the formula (D-A1) to (D-A3).

[wherein,

R^(p1), Rp² and R^(p3) each independently represent an alkyl group, acycloalkyl group, an alkoxy group, a cycloalkoxy group or a halogenatom. When a plurality of R^(p1) and R^(p2) are present, they may be thesame or different at each occurrence.

np1 represents an integer of 0 to 5, np2 represents an integer of 0 to3, and np3 represents 0 or 1. The plurality of np1 may be the same ordifferent.]

The group represented by the formula (D-B) is preferably a grouprepresented by the formula (D-B1) to (D-B3).

[wherein,

R^(p1), R^(p2) and R^(p3) each independently represent an alkyl group, acycloalkyl group, an alkoxy group, a cycloalkoxy group or a halogenatom. When a plurality of R^(p1) and R^(p2) are present, they may be thesame or different at each occurrence.

np1 represents an integer of 0 to 5, np2 represents an integer of 0 to3, and np3 represents 0 or 1. When a plurality of np1 and np2 arepresent, they may be the same or different at each occurrence.]

np1 is preferably 0 or 1, more preferably 1. np2 is preferably 0 or 1,more preferably 0. np3 is preferably 0.

R^(p1), R^(p2) and R^(p3) are preferably an alkyl group or a cycloalkylgroup.

The film production method of the present invention comprises an inkpreparation step, an ink storage step and a film formation step, asdescribed above. Further, the ink storage method of the presentinvention comprises an ink preparation step and a storage step, asdescribed above. Hereinafter, these steps will be explained in sequence.

<Ink Preparation Step>

The ink preparation step is a step of preparing an ink comprising ametal complex represented by the formula (1-A) or the formula (1-B), andan organic solvent.

[Metal Complex]

M is preferably an iridium atom because a light emitting device is moreexcellent in the external quantum efficiency.

E¹ is preferably a carbon atom.

When E^(11A) is a nitrogen atom and R^(11A) is present, it is preferablethat R^(11A) is an alkyl group, a cycloalkyl group, an aryl group, amonovalent heterocyclic group or a substituted amino group.

When E^(11A) is a carbon atom, R^(11A) is preferably a hydrogen atom, analkyl group, a cycloalkyl group, aryl group or a monovalent heterocyclicgroup, more preferably a hydrogen atom, an alkyl group, a cycloalkylgroup or an aryl group, further preferably a hydrogen atom, an alkylgroup or a cycloalkyl group.

When E^(12A) is a nitrogen atom and R^(12A) is present, it is preferablethat R^(12A) is an alkyl group, a cycloalkyl group, an aryl group, amonovalent heterocyclic group or a substituted amino group.

When E^(12A) is a carbon atom, R^(12A) is preferably a hydrogen atom, analkyl group, a cycloalkyl group, an aryl group or a monovalentheterocyclic group, more preferably a hydrogen atom, an alkyl group, acycloalkyl group or an aryl group, further preferably a hydrogen atom,an alkyl group or a cycloalkyl group.

When E^(13A) is a nitrogen atom and R^(13A) is present, it is preferablethat R^(13A) is an alkyl group, a cycloalkyl group, an aryl group, amonovalent heterocyclic group or a substituted amino group.

When E^(13A) is a carbon atom, R^(13A) is preferably a hydrogen atom, analkyl group, a cycloalkyl group, an aryl group or a monovalentheterocyclic group, more preferably a hydrogen atom, an alkyl group, acycloalkyl group or an aryl group, further preferably a hydrogen atom,an alkyl group or a cycloalkyl group.

R^(21A), R^(22A), R^(23A) and R^(24A) are each preferably a hydrogenatom, an alkyl group, a cycloalkyl group, an aryl group, a monovalentheterocyclic group or a substituted amino group, more preferably ahydrogen atom, an aryl group, a monovalent heterocyclic group or asubstituted amino group.

It is preferable that at least one of R^(11A), R^(12A), R^(13A),R^(21A), R^(22A), R^(23A) and R^(24A) has at least one selected from thegroup consisting of an aryl group, a monovalent heterocyclic group and asubstituted amino group, because a light emitting device is moreexcellent in the external quantum efficiency. These groups eachoptionally have a substituent.

When the ring R^(1A) is a diazole ring, a diazole ring in which E^(11A)is a nitrogen atom or a diazole ring in which E^(12A) is a nitrogen atomis preferable, the diazole ring in which E^(11A) is a nitrogen atombeing more preferable.

When the ring R^(1A) is a triazole ring, a triazole ring in whichE^(11A) and E^(12A) are each a nitrogen atom or a triazole ring in whichE^(11A) and E^(13A) are each a nitrogen atom is preferable, the triazolering in which E^(11A) and E^(12A) are each a nitrogen atom being morepreferable.

When the ring R^(1A) has an aryl group, a monovalent heterocyclic groupor a substituted amino group, it is preferable that R^(11A) or R^(12A)is an aryl group, a monovalent heterocyclic group or a substituted aminogroup, it is more preferable that R^(11A) is an aryl group, a monovalentheterocyclic group or a substituted amino group.

When the ring R^(2a) is a pyridine ring, a pyridine ring in whichE^(21A) is a nitrogen atom, a pyridine ring in which E^(22A) is anitrogen atom or a pyridine ring in which E^(23A) is a nitrogen atom ispreferable, the pyridine ring in which E^(22A) is a nitrogen atom beingmore preferable.

When the ring R^(2A) is a diazine ring, a diazine ring in which E^(21A)and E^(23A) are each a nitrogen atom or a diazine ring in which E^(22A)and E^(24A) are each a nitrogen atom is preferable, the diazine ring inwhich E^(22A) and E^(24A) are each a nitrogen atom being morepreferable.

The ring R^(2A) is preferably a benzene ring.

Examples of the anionic bidentate ligand represented by A¹-G¹-A² includeligands represented by the following formulae.

[wherein, * indicates a site binding to M.]

It is preferable that at least one selected from the group consisting ofR^(11B), R^(12B), R^(13B), R^(14B), R^(21B), R^(22B), R^(23B) andR^(24B) is an aryl group, a monovalent heterocyclic group or asubstituted amino group, because a light emitting device obtained byusing the film production method of the present invention is moreexcellent in the external quantum efficiency. These groups eachoptionally further have a substituent.

When the ring R^(1B) is a diazine ring, a diazine ring in which E^(11B)is a nitrogen atom or a diazine ring in which E¹³⁸ is a nitrogen atom ispreferable, the diazine ring in which E^(13B) is a nitrogen atom beingmore preferable.

R^(11B), R^(12B), R^(13B) and R^(14B) are each preferably a substituentselected from the group consisting of a hydrogen atom, an alkyl group, acycloalkyl group, an aryl group, a monovalent heterocyclic group and asubstituted amino group, more preferably a hydrogen atom, an aryl group,a monovalent heterocyclic group or a substituted amino group.

When the ring R^(1B) has a substituent selected from the groupconsisting of an aryl group, a monovalent heterocyclic group and asubstituted amino group, it is preferable that R^(11B), R^(12B) orR^(13B) is a substituent selected from the group consisting of an arylgroup, a monovalent heterocyclic, group and a substituted amino group,it is more preferable that R^(11B) or R^(13B) is a substituent selectedfrom the group consisting of an aryl group, a monovalent heterocyclicgroup and a substituted amino group, it is further preferable thatR^(11B) is an aryl group, a monovalent heterocyclic group or asubstituted amino group.

When the ring R^(2B) is a pyridine ring, a pyridine ring in whichE^(21B) is a nitrogen atom, a pyridine ring in which E^(22B) is anitrogen atom or a pyridine ring in which E^(23B) is a nitrogen atom ispreferable, the pyridine ring in which E^(22B) is a nitrogen atom beingmore preferable.

When the ring R^(2B) is a diazine ring, a diazine ring in which E^(21B)and E^(23B) are each a nitrogen atom or a diazine ring in which E^(22B)and E^(24B) are each a nitrogen atom is preferable, the diazine ring inwhich E^(22B) and E^(24B) are each a nitrogen atom being morepreferable.

The ring R^(2B) is preferably a benzene ring.

R^(21B), R^(22B), R^(23B) and R^(24B) are each preferably a groupselected from the group consisting of a hydrogen atom, an alkyl group, acycloalkyl group, an aryl group, a monovalent heterocyclic group and asubstituted amino group, more preferably a group selected from the groupconsisting of a hydrogen atom, an aryl group, a monovalent heterocyclicgroup and a substituted amino group.

When the ring R^(2B) has a substituent selected from the groupconsisting of an aryl group, a monovalent heterocyclic group and asubstituted amino group, it is preferable that R^(22B) or R^(23B) is asubstituent selected from the group consisting of an aryl group, amonovalent heterocyclic group and a substituted amino group, it is morepreferable that R^(22B) is an aryl group, a monovalent heterocyclicgroup or a substituted amino group.

The metal complex represented by the formula (1-A) is preferably a metalcomplex represented by the formula (1-A1), the formula (1-A2), theformula (1-A3) or the formula (1-A4), more preferably a metal complexrepresented by the formula (1-A1) or the formula (1-A2), furtherpreferably a metal complex represented by the formula (1-A1).

The metal complex represented by the formula (1-B) is preferably a metalcomplex in which E^(11B), E^(12B), E^(13B), E^(14B), E^(21B), E^(22B),E^(23B) and E^(24B) are each a carbon atom, more preferably a metalcomplex in which the ring R^(1B) is a condensed ring in addition tothat, further preferably a metal complex represented by the formula(1-B1), the formula (1-B2) or the formula (1-B3), particularlypreferably a metal complex represented by the formula (1-B1).

The metal complex is preferably a metal complex represented by theformula (1-A).

The metal complex represented by the formula (1-A) or formula (1-B)includes, for example, metal complexes represented by COM-1 to COM-20.

It is preferable that the metal complex represented by the formula (1-A)or formula (1-B) has a dendron as a substituent, because solubility inan organic solvent and the external quantum efficiency of a lightemitting device are excellent.

The metal complex represented by the formula (1-A) or formula (1-B) canbe synthesized, for example, according to methods described in JapaneseTranslation of PCT International Application Publication (JP-T) No.2004-530254, Japanese Unexamined Patent Application Publication (JP-A)No. 2008-179617, JP-A No. 2011-105701, JP-T No. 2007-504272, JP-A No.2013-147449 and JP-A No. 2013-147450.

In the ink before storage, the content of metal complexes having amolecular weight larger by 16, 32 or 48 than that of the metal complexrepresented by the formula (1-A) or the formula (1-B) according to thearea percentage value determined by liquid chromatography is usually 0.6or less, preferably 0.3 or less, more preferably 0.1 or less when thecontent of the metal complex represented by the formula (1-A) or theformula (1-B) according to the area percentage value determined byliquid chromatography is taken as 100.

In the ink after storage, the content of metal complexes having amolecular weight larger by 16, 32 or 48 is 0.6 or less, preferably 0.51or less.

In the ink preparation step, the metal complexes represented by theformula (1-A) or the formula (1-B) may be used each singly or incombination of two or more thereof.

[Organic Solvent]

The organic solvent used for the film production method of the presentinvention is usually a solvent capable of dissolving or uniformlydispersing the solid component in the ink. The organic solvent includes,for example, chlorine-based solvents such as 1,2-dichloroethane,1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene; ethersolvents such as THE, dioxane, anisole and 4-methylanisole; aromatichydrocarbon solvents such as toluene, xylene, mesitylene, ethylbenzene,n-hexylbenzene and cyclohexyl benzene; aliphatic hydrocarbon solventssuch as cyclohexane, methylcyclohexane, n-heptane, n-hexane, n-heptane,n-octane, n-nonane, n-decane, n-dodecane and bicyclohexyl; ketonesolvents such as acetone, methyl ethyl ketone, cyclohexanone andacetophenone; ester solvents such as ethyl acetate, butyl acetate, ethylcellosolve acetate, methyl benzoate and phenyl acetate; polyhydricalcohol solvents such as ethylene glycol, glycerin and 1,2-hexanediol;alcohol solvents such as isopropyl alcohol and cyclohexanol; sulfoxidesolvents such as dimethyl sulfoxide; amide solvents such asN-methyl-2-pyrrolidone and N,N-dimethylformamide, and preferred areether solvents and aromatic hydrocarbon solvents.

In the ink preparation step, the organic solvents may be used eachsingly or in combination of two or more thereof.

In the ink, the blending amount of the organic solvent is usually 1000to 100000 parts by weight, preferably 2000 to 20000 parts by weight withrespect to 100 parts by weight of the total solid content.

The viscosity of the ink may be adjusted depending on the type of theprinting method, and when applied to a printing method in which asolution passes through a discharge apparatus such as an inkjet printmethod, the viscosity is preferably 1 to 25 mPa·s at 25° C. becauseclogging and flight deflection at discharge are less likely to occur.

The ink prepared in the ink preparation step may further comprise atleast one material selected from the group consisting of a hostmaterial, a hole transporting material, a hole injection material, anelectron transporting material, an electron injection material, a lightemitting material and an antioxidant. These materials each may be usedsingly or in combination of two or more thereof.

[Host Material]

When the ink comprises a host material having at least one functionselected from the group consisting of hole injectability, holetransportability, electron injectability and electron transportability,the external quantum efficiency of a light emitting device becomesexcellent.

When the ink comprises a host material, the content of the metal complexrepresented by the formula (1-A) or the formula (1-B) is usually 0.05 to80 parts by weight, preferably 0.1 to 50 parts by weight, morepreferably 0.5 to 40 parts by weight with respect to 100 parts by weightof the sum of the metal complex represented by the formula (1-A) or theformula (1-B) and the host material.

It is preferable that the lowest excited triplet state (T₁) of the hostmaterial is at energy level equivalent to or higher than T₁ of the metalcomplex represented by the formula (1-A) or the formula (1-B) becausethe external quantum efficiency of a light emitting device is excellent.

The host material is classified into low molecular weight compounds (lowmolecular weight host) and polymer compounds (polymer host), and the lowmolecular weight host is preferable.

[Low Molecular Weight Host]

The low molecular weight host is preferably a compound represented bythe formula (H-1).

Ar^(H1) and Ar^(H2) are preferably a phenyl group, a fluorenyl group, aspirobifluorenyl group, a pyridyl group, a pyrimidinyl group, atriazinyl group, a quinolinyl group, an isoquinolinyl group, a thienylgroup, a benzothienyl group, a dibenzothienyl group, a furyl group, abenzofuryl group, a dibenzofuryl group, a pyrrolyl group, an indolylgroup, an azaindolyl group, a carbazolyl group, an azacarbazolyl group,a diazacarbazolyl group, a phenoxazinyl group or a phenothiazinyl group,more preferably a phenyl group, a pyridyl group, a carbazolyl group oran azacarbazolyl group, further preferably a group represented by theabove-described formula (TDA-1) or the above-described formula (TDA-3),particularly preferably a group represented by the above-describedformula (TDA-3), and these groups each optionally have a substituent.

The substituent which Ar^(H1) and Ar^(H2) optionally have is preferablya halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, acycloalkoxy group, an aryl group or a monovalent heterocyclic group,more preferably an alkyl group, a cycloalkoxy group, an alkoxy group orcycloalkoxy group, further preferably an alkyl group or cycloalkoxygroup, and these groups each optionally further have a substituent.

n^(H1) is preferably 1. n^(H2) is preferably 0.

n^(H3) is preferably an integer of 0 to 5, more preferably an integer of1 to 3, further preferably 1.

n^(H11) is preferably an integer of 1 to 5, more preferably an integerof 1 to 3, further preferably 1.

R^(H11) is preferably a hydrogen atom, an alkyl group, a cycloalkylgroup, an aryl group or a monovalent heterocyclic group, more preferablya hydrogen atom, an alkyl group or a cycloalkyl group, furtherpreferably a hydrogen atom or an alkyl group, and these groups eachoptionally have a substituent.

L^(H1) is preferably an arylene group or a divalent heterocyclic group.

L^(H1) is preferably a group represented by the formula (A-1) to (A-3),the formula (A-8) to (A-10), the formula (AA-1) to (AA-6), the formula(AA-10) to (AA-21) or the formula (AA-24) to (AA-34), more preferably agroup represented by the formula (A-1), the formula (A-2), the formula(A-8), the formula (A-9), the formula (AA-2), the formula (AA-4) or theformula (AA-10) to (AA-15), further preferably a group represented bythe formula (A-1), the formula (A-2), the formula (A-8), the formula(AA-2), the formula (AA-4), the formula (AA-10), the formula (AA-12) orthe formula (AA-14), particularly preferably a group represented by theformula (A-1), the formula (A-2), the formula (AA-2), the formula (AA-4)or the formula (AA-14).

The substituent which L^(H1) optionally has is preferably a halogenatom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxygroup, an aryl group or a monovalent heterocyclic group, more preferablyan alkyl group, an alkoxy group, an aryl group or a monovalentheterocyclic group, further preferably an alkyl group, an aryl group ora monovalent heterocyclic group, and these groups optionally furtherhave a substituent.

L^(H21) is preferably a single bond or an arylene group optionallyhaving a substituent, more preferably a single bond.

The definition and examples of the arylene group or the divalentheterocyclic group represented by L^(H21) are the same as the definitionand examples of the arylene group or the divalent heterocyclic grouprepresented by L^(H1).

R^(H21) is preferably an aryl group or a monovalent heterocyclic group,and these groups each optionally have a substituent. The definition andexamples of the aryl group and the monovalent heterocyclic grouprepresented by R^(H21) are the same as the definition and examples ofthe aryl group and the monovalent heterocyclic group represented byAr^(H1) and Ar^(H2). The definition and examples of the substituentwhich R^(H21) may optionally has are the same as the definition andexamples of the substituent which Ar^(H1) and Ar^(H2) optionally have.

The compound represented by the formula (H-1) is preferably a compoundrepresented by the formula (H-2).

[wherein, Ar^(H1), Ar^(H2), n^(H3) and L^(H1) represent the same meaningas described above.]

As the compound represented by the formula (H-1), compounds representedby the following formulae (H-101) to (H-119) are exemplified.

[Polymer Host]

The polymer host includes, for example, polymer compounds as a holetransporting material described later and polymer compounds as anelectron transporting material described later. The polymer host ispreferably a polymer compound comprising a constitutional unitrepresented by the formula (Y).

The arylene group represented by Ar¹¹ is more preferably a grouprepresented by the formula (A-1), the formula (A-2), the formula (A-6)to (A-10), the formula (A-19) or the formula (A-20), further preferablya group represented by the formula (A-1), the formula (A-2), the formula(A-1), the formula (A-9) or the formula (A-19), and these groups eachoptionally have a substituent.

The divalent heterocyclic group represented by Ar¹¹ is more preferably agroup represented by the formula (AA-1) to (AA-4), the formula (AA-10)to (AA-15), the formula (AA-18) to (AA-21), the formula (AA-33) or theformula (AA-34), further preferably a group represented by the formula(AA-4), the formula (AA-10), the formula (AA-12), the formula (AA-14) orthe formula (AA-33), and these groups each optionally have asubstituent.

The more preferable range and the further preferable range of thearylene group and the divalent heterocyclic group in the divalent groupin which at least one arylene group and at least one divalentheterocyclic group are bonded directly to each other represented byAr^(Y1) are the same as the more preferable range and the furtherpreferable range of the arylene group and the divalent heterocyclicgroup represented by Ar^(Y1) described above, respectively.

“The divalent group in which at least one arylene group and at least onedivalent heterocyclic group are bonded directly to each other” includes,for example, groups represented by the following formulae, and each ofthem optionally has a substituent.

[wherein, R^(XX) represents a hydrogen atom, an alkyl group, acycloalkyl group, an aryl group or a monovalent heterocyclic group andthese groups each optionally have a substituent.]

R^(XX) is preferably an alkyl group, a cycloalkyl group or an arylgroup, and these groups each optionally have a substituent.

The substituent which the group represented by Ar^(Y1) optionally has ispreferably an alkyl group, a cycloalkyl group or an aryl group, andthese groups each optionally further have a substituent.

The constitutional unit represented by the formula (Y) includes, forexample, constitutional units represented by the formulae (Y-1) to(Y-10), and from the standpoint of the luminance life of the lightemitting device produced by using the composition comprising the polymerhost and the metal complex of the present invention preferable areconstitutional units represented by the formulae (Y-1) to (Y-3), fromthe standpoint of electron transportability preferable areconstitutional units represented by the formulae (Y-4) to (Y-1), andfrom the standpoint of hole transportability preferable areconstitutional units represented by the formulae (Y-8) to (Y-10).

[wherein, R^(Y1) represents a hydrogen atom, an alkyl group, acycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group ora monovalent heterocyclic group, and these groups each optionally have asubstituent. The plurality of R^(Y1) may be the same or different, andadjacent R^(Y1) s may be combined together to form a ring together withthe carbon atoms to which they are attached.]

[wherein, R^(Y1) represents the same meaning as described above. X^(Y1)represents a group represented by —C(R^(Y2))₂, —C(R^(Y2))═C(R^(X2))— or—C(R^(Y2))₂—C(R^(Y2))₂—R^(Y2) represents a hydrogen atom, an alkylgroup, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an arylgroup or a monovalent heterocyclic group and these groups eachoptionally have a substituent. The plurality of R^(Y2) may be the sameor different, and these R^(Y2) s may be combined together to form a ringtogether with the carbon atoms to which they are attached.]

R^(Y2) is preferably an alkyl group, a cycloalkyl group, an aryl groupor a monovalent heterocyclic group, more preferably an alkyl group acycloalkyl group or an aryl group, and these groups each optionally havea substituent.

Regarding the combination of two R^(Y2)s in the group represented by—C(R^(Y2))₂— in X^(Y1), it is preferable than the both are an alkylgroup or a cycloalkyl group, the both are an aryl group, the both are amonovalent heterocyclic group, or one is an alkyl group or a cycloalkylgroup and the other is an aryl group or a monovalent heterocyclic group,it is more preferable that one is an alkyl group or cycloalkyl group andthe other is an aryl group, and these groups each optionally have asubstituent. The two groups R^(Y2) may be combined together to form aring together with the atoms to which they are attached, and when thegroups R^(Y2) form a ring, the group represented by —C(R^(Y2))₂ ispreferably a group represented by the formula (Y-A1) to (Y-A5), morepreferably a group represented by the formula (Y-A4), and these groupseach optionally have a substituent.

Regarding the combination of two R^(Y2) s in the group represented by—C(R^(Y2))═C(R^(Y2))—in X^(Y1), it is preferable that the both are analkyl group or cycloalkyl group, or one is an alkyl group or acycloalkyl group and the other is an aryl group, and these groups eachoptionally have a substituent.

Four R^(Y2) s in the group represented by —C(R^(Y2))₂—C(R^(Y2)) 2—inX^(Y1) are preferably an alkyl group or a cycloalkyl group eachoptionally having a substituent. The plurality of R^(Y2) may be combinedtogether to form a ring together with the atoms to which they areattached, and when the groups R^(Y2) form a ring, the group representedby —C(R^(Y2))₂—C(R^(Y2))₂—is preferably a group represented by theformula (Y-B1) to (Y-B5), more preferably a group represented by theformula (Y-B3), and these groups each optionally have a substituent.

[wherein, R^(Y2) represents the same meaning as described above.]

[wherein, R^(Y1) and X^(Y1) represent the same meaning as describedabove.]

[wherein, R^(Y1) represents the same meaning as described above. R^(Y3)represents a hydrogen atom, an alkyl group, a cycloalkyl group, analkoxy group, a cycloalkoxy group, an aryl group or a monovalentheterocyclic group and these groups each optionally have a substituent.]

R^(Y3) is preferably an alkyl group, a cycloalkyl group, an alkoxygroup, a cycloalkoxy group, an aryl group or a monovalent heterocyclicgroup, more preferably an aryl group, and these groups each optionallyhave a substituent.

[wherein, R^(Y1) represents the same meaning as described above. R^(Y4)represents a hydrogen atom, an alkyl group, a cycloalkyl group, analkoxy group, a cycloalkoxy group, an aryl group or a monovalentheterocyclic group, and these groups each optionally have asubstituent.]

R^(Y4) is preferably an alkyl group, a cycloalkyl group, an alkoxygroup, a cycloalkoxy group, an aryl group or a monovalent heterocyclicgroup, more preferably an aryl group, and these groups each optionallyhave a substituent.

The constitutional unit represented by the formula (Y) includes, forexample, a constitutional unit composed of an arylene group representedby the formula (Y-101) to (Y-121), a constitutional unit composed of adivalent heterocyclic group represented by the formula (Y-201) to(Y-206), and a constitutional unit composed of a divalent group in whichat least one arylene group and at least one divalent heterocyclic groupare bonded directly to each other represented by the formula (Y-301) to(Y-304).

The amount of the constitutional unit represented by the formula (Y) inwhich Ar^(Y1) is an arylene group is preferably 0.5 to 80 mol %, morepreferably 30 to 60 mol % with respect to the total amount ofconstitutional units contained in a polymer compound, because theluminance life of a light emitting device is excellent.

The amount of the constitutional unit represented by the formula (Y) inwhich Ar^(Y1) is a divalent heterocyclic group or a divalent group inwhich at least one arylene group and at least one divalent heterocyclicgroup are bonded directly to each other is preferably 0.5 to 30 mol %,more preferably 3 to 20 mol % with respect to the total amount ofconstitutional units contained in a polymer compound, because the chargetransportability of a light emitting device is excellent.

The constitutional unit represented by the formula (Y) may be containedonly singly or two or more units thereof may be contained in the polymerhost.

It is preferable that the polymer host further comprises aconstitutional unit represented by the following formula (X), becausehole transportability is excellent.

[wherein, a^(X1) and a^(X2) each independently represent an integer of 0or more. Ar^(X1) and Ar^(X3) each independently represent an arylenegroup or a divalent heterocyclic group, and these groups each optionallyhave a substituent. Ar^(X2) and Ar^(X4) each independently represent anarylene group, a divalent heterocyclic group or a divalent group inwhich at least one arylene group and at least one divalent heterocyclicgroup are bonded directly to each other, and these groups eachoptionally have a substituent. R^(X1), R^(X2) and R^(X3) eachindependently represent a hydrogen atom, an alkyl group, a cycloalkylgroup, an aryl group or a monovalent heterocyclic group, and thesegroups each optionally have a substituent.]

a^(X1) is preferably 2 or less, more preferably 1, because the luminancelife of a light emitting device is excellent.

a^(X2) is preferably 2 or less, more preferably 0, because the luminancelife of a light emitting device is excellent.

R^(X1), R^(X2) and R^(X3) are preferably an alkyl group, a cycloalkylgroup, an aryl group or a monovalent heterocyclic group, more preferablyan aryl group, and these groups each optionally have a substituent.

The arylene group represented by Ar^(X1) and Ar^(X3) is more preferablya group represented by the formula (A-1) or the formula (A-9), furtherpreferably a group represented by the formula (A-1), and these groupseach optionally have a substituent.

The divalent heterocyclic group represented by Ar^(X1) and Ar^(X3) ismore preferably a group represented by the formula (AA-1), the formula(AA-2) or the formula (AA-7) to (AA-26), and these groups eachoptionally have a substituent.

Ar^(X1) and Ar^(X3) are preferably an arylene group optionally having asubstituent.

The arylene group represented by Ar^(X2) and Ar^(X4) is more preferablya group represented by the formula (A-1), the formula (A-6), the formula(A-1), the formula (A-9) to (A-11) or the formula (A-19), and thesegroups each optionally have a substituent.

The more preferable range of the divalent heterocyclic group representedby Ar^(X2) and Ar^(X4) is the same as the more preferable range of thedivalent heterocyclic group represented by Ar^(X1) and Ar^(X3).

The more preferable range and the further preferable range of thearylene group and the divalent heterocyclic group in the divalent groupin which at least one arylene group and at least one divalentheterocyclic group are bonded directly to each other represented byAr^(X2) and Ar^(X4) are the same as the more preferable range and thefurther preferable range of the arylene group and the divalentheterocyclic group represented by Ar^(X1) and Ar^(X3), respectively.

The divalent group in which at least one arylene group and at least onedivalent heterocyclic group are bonded directly to each otherrepresented by Ar^(X2) and Ar^(X4) includes the same groups as thedivalent group in which at least one arylene group and at least onedivalent heterocyclic group are bonded directly to each otherrepresented by Ar^(Y1) in the formula (Y).

Ar^(X2) and Ar^(X4) are preferably an arylene group optionally having asubstituent.

The substituent which the group represented by Ar^(X1) to Ar^(X4) andR^(X1) to R^(X3) optionally has is preferably an alkyl group, acycloalkyl group or an aryl group, and these groups each optionallyfurther have a substituent.

The constitutional unit represented by the formula (X) is preferably aconstitutional unit represented by the formula (X-1) to (X-7), morepreferably a constitutional unit-represented by the formula (X-1) to(X-6), further preferably a constitutional unit represented by theformula (X-3) to (X-6).

[wherein, R^(X4) and R^(X5) each independently represent a hydrogenatom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxygroup, an aryl group, an aryloxy group, a halogen atom, a monovalentheterocyclic group or a cyano group, and these groups each optionallyhave a substituent. The plurality of R^(X4) may be the same ordifferent. The plurality of R^(X5) may be the same or different, andadjacent groups R^(X5) may be combined together to form a ring togetherwith the carbon atoms to which they are attached.]

The amount of the constitutional unit represented by the formula (X) ispreferably 0.1 to 50 mol %, more preferably 1 to 40 mol %, furtherpreferably 5 to 30 mol % with respect to the total amount ofconstitutional units contained in a polymer host, because holetransportability is excellent.

The constitutional unit represented by the formula (X) includes, forexample, constitutional units represented by the formulae (X1-1) to(X1-11), preferably constitutional units represented by the formulae(X1-3) to (X1-10).

The constitutional unit represented by the formula (X) may be containedonly singly or two or more units thereof may be contained in the polymerhost.

Examples of the polymer host include polymer compounds (P-1) to (P-6) inTable 1. “Other” constitutional unit denotes a constitutional unit otherthan the constitutional unit represented by the formula (Y) and theconstitutional unit represented by the formula (X).

TABLE 1 constitutional unit and mole fraction thereof formula (Y)formula (X) formulae formulae formulae formulae (Y-1) to (Y-4) to (Y-8)to (X-1) to polymer (Y-3) (Y-7) (Y-10) (X-7) other compound p q r s t(P-1) 0.1 to 0.1 to 0 0 0 to 99.9 99.9 30 (P-2) 0.1 to 0 0.1 to 0 0 to99.9 99.9 30 (P-3) 0.1 to 0.1 to 0 0.1 to 0 to 99.8 99.8 99.8 30 (P-4)0.1 to 0.1 to 0.1 to 0 0 to 99.8 99.8 99.8 30 (P-5) 0.1 to 0 0.1 to 0.1to 0 to 99.8 99.8 99.8 30 (P-6) 0.1 to 0.1 to 0.1 to 0.1 to 0 to 99.799.7 99.7 99.7 30[In the table, p, q, r, s and t represent the mole fraction of eachconstitutional unit, p+q+r+s+t=100, and 100≥p+q+r+s≥70. Otherconstitutional unit denotes a constitutional unit other than theconstitutional unit represented by the formula (Y) and theconstitutional unit represented by the formula (X).]

The polymer host may be any of a block copolymer, a random copolymer, analternating copolymer or a graft copolymer, and may also be anotherembodiment, and is preferably a copolymer produced by copolymerizing aplurality of raw material monomers.

[Hole Transporting Material]

The hole transporting material is classified into low molecular weightcompounds and polymer compounds, and may have a crosslinkable group.

As the low molecular weight compound, for example, aromatic amines suchas 1,1-bis(di-4-tolylaminophenyl)cyclohexane (TAPC),

-   N,N′-diphenyl-N,N′-[bis(3-methylphenyl)]-[1,1′-biphenyl]-4,    4′-diamine (TPD),-   (N,N′-di-α-naphthyl-N,N′-diphenyl)-benzidine (α-NPD) and-   4,4′,4″-tris(3-methylphenylphenylamino)triphenylamine (MTDATA) are    mentioned.

The polymer compound includes, for example, polyvinylcarbazole andderivatives thereof; polyarylenes having an aromatic amine structure inthe side chain or main chain and derivatives thereof. The polymercompound may be a compound to which an electron accepting site isbonded. The electron accepting site includes, for example, fullerene,tetrafluorotetracyanoquinodimethane, tetracyanoethylene andtrinitrofluorenone.

In the ink, the blending amount of a hole transporting material isusually 1 to 1000000 parts by weight, preferably 10 to 100000 parts byweight with respect to 100 parts by weight of the metal complexrepresented by the formula (1-A) or the formula (1-B).

[Hole Injection Material]

The hole injection material is classified into low molecular weightcompounds and polymer compounds, and may have a crosslinkable group.

The low molecular weight compound includes, for example, metalphthalocyanines such as copper phthalocyanine; and oxides of metals suchas molybdenum and tungsten.

The polymer compound includes, for example, electrically conductivepolymers such as polyaniline, polythiophene and polypyrrole.

In the ink, the blending amount of a hole injection material is usually1 to 1000000 parts by weight, preferably 10 to 100000 parts by weightwith respect to 100 parts by weight of the metal complex represented bythe formula (1-A) or the formula (1-B).

[Electron Transporting Material]

The electron transporting material is classified into low molecularweight compounds and polymer compounds. The electron transportingmaterial may have a crosslinkable group.

The low molecular weight compound includes, for example, metal complexeshaving 8-hydroxyquinoline as a ligand, oxadiazole, anthraquinodimethane,benzoquinone, naphthoquinone, anthraquinone,tetracyanoanthraquinodimethane, fluorenone, diphenyldicyanoethylene anddiphenoquinone, and derivatives thereof.

The polymer compound includes, for example, polyphenylene, polyfluorene,and derivatives thereof.

In the ink, the blending amount of an electron transporting material isusually 1 to 1000000 parts by weight, preferably 1 to 100000 parts byweight with respect to 100 parts by weight of the metal complexrepresented by the formula (1-A) or the formula (1-B).

[Electron Injection Material]

The electron injection material is classified into low molecular weightcompounds and polymer compounds. The electron injection material mayhave a crosslinkable group.

The low molecular weight compound includes, for examples, metalfluorides such as lithium fluoride, sodium fluoride, cesium fluoride andpotassium fluoride.

The polymer compound includes, for example, polyphenylenevinylene,polythienylenevinylene, polyquinoline and polyquinoxaline, andderivatives thereof, and the like.

In the ink, the blending amount of an electron injection material isusually 1 to 1000000 parts by weight, preferably 1 to 100000 parts byweight with respect to 100 parts by weight of the metal complexrepresented by the formula (1-A) or the formula (1-B).

[Light Emitting Material]

The light emitting material (different from the metal complexrepresented by the formula (1-A) or the formula (1-B)) is classifiedinto low molecular weight compounds and polymer compounds. The lightemitting material may have a crosslinkable group.

The low molecular weight compound includes, for example, naphthalene andderivatives thereof, anthracene and derivatives thereof, and peryleneand derivatives thereof.

The polymer compound includes, for example, polymer compounds such as aphenylene group, a naphthalenediyl group, an anthracenediyl group, afluorenediyl group, a phenanthrenediyl group, a dihydrophenanthrenediylgroup, a carbazolediyl group, a phenoxazinediyl group, aphenothiazinediyl group, an anthracenediyl group and a pyrenediyl, andcopolymers of them with aromatic amines.

In the ink, the blending amount of a light emitting material is usually0.01 to 1000000 parts by weight, preferably 0.1 to 100000 parts byweight with respect to 100 parts by weight of the metal complexrepresented by the formula (1-A) or the formula (1-B).

[Antioxidant]

The antioxidant may be a compound soluble in an organic solvent which isthe same as the solvent in which the metal complex represented by theformula (1-A) or the formula (1-B) is soluble and which does not inhibitlight emission and charge transportation, and includes, for example,phenol antioxidants and phosphorus-based antioxidants.

In the ink, the blending amount of an antioxidant is usually 0.01 to 10parts by weight, preferably 0.1 to 5 parts by weight with respect to 100parts by weight of the metal complex represented by the formula (1-A) orthe formula (1-B).

<Ink Storage Step•Storage Step>

The ink storage step is a step of storing the ink prepared in the inkpreparation step for 3 days or more under light shielding. The storagestep is a step of storing the ink prepared in the ink preparation stepfor three days or more, and the storage step is preferably performedunder light shielding. Hereinafter, the ink storage step and the storagestep are collectively referred to simply as “ink storage step”.

The storage time in the ink storage step is preferably 1 week or morebecause the external quantum efficiency of a light emitting device isexcellent. The storage time in the ink storage step is preferably 3years or less, more preferably 1 year or less, further preferably 1 to 5weeks, particularly preferably 3 to 5 weeks.

In the ink storage step, the ink may be stored in a brown glass bottleor in a light-shielding sealed container made of a metal or the like, orplaced in a transparent container and stored under light shielding, andit is preferable that the ink is stored under complete light shielding.

In the ink storage step, the atmosphere is not limited and an airatmosphere may be permissible, but an atmosphere of an inert gas such asa nitrogen gas and an argon gas is preferable.

In the ink storage step, the storage temperature is usually 0° C. to 50°C., preferably 10° C. to 30° C.

It is preferable that Cb[M], Cb[M+16n], Ca[M] and Ca[M+16n] in theformula (1) satisfy the formula (1′).

0.3≤(Ca[M+16n]/Ca[M])/(Cb[M+16n]/Cb[M])≤10  (1′)

<Film Formation Step>

The film formation step is a step of forming a film by an applicationmethod using an ink stored in the ink storage step and in which thetotal content of metal complexes having a molecular weight larger by 16,32 or 48 than that of the metal complex represented by the formula (1-A)or the formula (1-B) according to the area percentage value is 0.6 orless when the content of the metal complex represented by the formula(1-A) or the formula (1-B) according to the area percentage value istaken as 100.

The total content of metal complexes having a molecular weight larger by16, 32 or 48 than that of the metal complex represented by the formula(1-A) or the formula (1-B) according to the area percentage value,stored in the ink storage step, is preferably 0.01 to 0.52, morepreferably 0.02 to 0.10 when the content of the metal complexrepresented by the formula (1-A) or the formula (1-B) according to thearea percentage value is taken as 100.

When a plurality of the metal complexes represented by the formula (1-A)or the formula (1-B) are contained in the ink used in the film formationstep, the content of the metal complex contained in the largest amountis taken as 100. On the other hand, when a plurality of metal complexeshaving a molecular weight larger by 16, 32, or 48 than that of the metalcomplex represented by the formula (1-A) or the formula (1-B) arecontained, the total content is adopted.

The metal complex having a molecular weight larger by 16, 32 or 48 thanthat of the metal complex represented by the formula (1-A) or theformula (1-B) is a component that can be generated by an external factoror an internal factor in the metal complex production step, the inkpreparation step and the ink storage step.

The amount of the metal complex represented by the formula (1-A) or theformula (1-B) and the metal complex having a molecular weight larger by16, 32 or 48 than that of the metal complex represented by the formula(1-A) or the formula (1-B) in the ink used in the film formation stepcan be analyzed by liquid chromatography (LC). The metal complex havinga molecular weight larger by 16, 32 or 48 than that of the metal complexrepresented by the formula (1-A) or the formula (1-B) in the ink can bedetected by LC-MS. Note that this analysis and detection are performedafter the ink storage step.

The application method for the film formation step includes, forexample, a spin coat method, a casting method, a micro gravure coatmethod, a gravure coat method, a bar coat method, a roll coat method, awire bar coat method, a dip coat method, a spray coat method, a screenprinting method, a flexo printing method, an offset printing method, aninkjet printing method, a capillary coat method and a nozzle coatmethod.

In the film formation step, after applying the ink to a substrate or thelike by an application method, an organic solvent is removed asnecessary. As a method for removing an organic solvent, for example,natural drying and heating are mentioned.

The film formation step may be performed under an air atmosphere, but itis preferable to perform it under light shielding and under an inert gasatmosphere.

<Others>

The film produced by the film production method of the present inventionis useful for a light emitting device. The constitution of a lightemitting device comprises, for example, electrodes consisting of ananode and a cathode, and a light emitting layer composed of theabove-described film disposed between the electrodes. The light emittingdevice may additionally comprise a hole transporting layer, an electrontransporting layer, a light emitting layer, a hole injection layer, anelectron injection layer and the like between the electrodes.

It is preferable that the material used for a hole transporting layer,an electron transporting layer and a light emitting layer has acrosslinkable group to avoid dissolution of the material in a solvent inwhich a layer adjacent to the hole transporting layer, the electrontransporting layer and the light emitting layer is dissolved in formingthe adjacent layer. After forming each layer using the material having acrosslinkable group, the crosslinkable group can be cross-linked toinsolubilize the layer.

The method of forming each layer includes, for example, a vacuum vapordeposition method from powder, a method by film formation from solutionor melted state. The order, number and thickness of the layers to belaminated are adjusted in view of the external quantum efficiency andthe luminance life.

The substrate in the light emitting device may be a substrate on which asingle-layered or laminated electrode can be formed and which does notchemically change when forming an organic layer and, for example, is asubstrate made of a material such as glass, plastic and silicon. In thecase of an opaque substrate, it is preferred that the electrode farthestfrom the substrate is transparent or semi-transparent.

The anode material includes, for example, electrically conductive metaloxides and semi-transparent metals, preferably, indium oxide, zincoxide, tin oxide; electrically conductive compounds such asindium•tin•oxide (ITO) and indium•zinc•oxide; a complex of silver andpalladium and copper (APC); NESA, gold, platinum, silver and copper.

The cathode material includes, for example, metals such as lithium,sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium,strontium, barium, aluminum, zinc and indium; alloys composed of two ormore of them; alloys composed of at least one of them and at least oneof silver, copper, manganese, titanium, cobalt, nickel, tungsten andtin; and graphite and graphite intercalation compounds.

Examples

The present invention will be illustrated further in detail by examplesbelow, but the present invention is not limited to these examples.

In the examples, the polystyrene-equivalent number average molecularweight (Mn) and the polystyrene-equivalent weight average molecularweight (Mw) of a polymer compound were measured by size exclusionchromatography (SEC) (manufactured by Shimadzu Corp., trade name: LC-10Avp). SEC measurement conditions are as described below.

[Measurement Condition]

The polymer compound to be measured was dissolved in THF at aconcentration of about 0.05 wt %, and 10 μL of the solution was injectedinto SEC. As the mobile phase of SEC, THF was used and allowed to flowat a flow rate of 2.0 mL/min. As the column, PLgel MIXED-B (manufacturedby Polymer Laboratories) was used. As the detector, UV-VIS detector(manufactured by Shimadzu Corp., trade name: SPD-10Avp) was used.

NMR measurement was conducted by the following method.

Approximately 10 mg of a measurement sample was dissolved in about 0.7mL of a deuterated solvent and NMR was measured using an NMR apparatus(trade name: MERCURY 300, manufactured by Varian, Inc.).

As an indicator of the purity of the compound, the high performanceliquid chromatography (HPLC) area percent value was used. Unlessotherwise specified, this value is a value at 254 nm in HPLC (tradename: LC-20A, manufactured by Shimadzu Corporation). In this case, thecompound to be measured was dissolved in an ink solvent so as to give aconcentration of 0.01 to 1.0% by weight, preferably 0.01 to 0.2% byweight, and the solution was injected in an amount of 1 to 10 μLdepending on the concentration into HPLC. Samples for HPLC were preparedwithin 30 minutes, stored under light shielding, and NMR was measuredwithin 10 hours after sample preparation. As the mobile phase of HPLC,acetonitrile and tetrahydrofuran were used, and the solution was flowedat a flow rate of 1 mL/min at gradient ofacetonitrile/tetrahydrofuran=100/0 to 0/100 (volume ratio). As thecolumn, SUMIPAX ODS Z-CLUE (manufactured by Sumika Chemical AnalysisService, Ltd.) or an ODS column having the equivalent performance wasused. As the detector, a photodiode array detector (trade name:SPD-M20A, manufactured by Shimadzu Corporation,) was used.

Liquid chromatograph mass spectrometry (LC-MS) was conducted by thefollowing method.

A measurement sample was dissolved in an ink solvent so as to give aconcentration of about 2 mg/mL, and about 1 μL of the solution wasinjected into LC-MS (trade name: 1100LCMSD, manufactured by AgilentTechnologies). Samples for LC-MS were prepared within 30 minutes, storedunder light shielding, and LC-MS was measured within 10 hours aftersample preparation. As the mobile phase for LC-MS, acetonitrile and THFwere used while changing the ratio thereof, and the solution was flowedat a flow rate of 0.2 ml/min. As the column, SUMIPAX ODS Z-CLUE (ϕ4.6×250 mm, 3 jam, manufactured by Sumika Chemical Analysis Service,Ltd.) was used.

<Synthesis Example 1> Synthesis of Monomers 1, 4

A monomer 1 was synthesized according to the synthesis method describedin Dalton Trans., 2011, 40, 2433.

A monomer 4 was synthesized according to the synthesis method describedin International Publication WO 2005/049546.

<Synthesis Example 2> Synthesis of Monomer 2

A gas in a flask equipped with a stirrer was purged with a nitrogen gas,then, a compound Ma2 (64.6 g) and tetrahydrofuran (615 mL) were added,and the mixture was cooled down to −70° C. Into this, a n-butyllithiumhexane solution (1.6 M, 218 mL) was dropped over a period of 1 hour,then, the mixture was stirred at −70° C. for 2 hours. To this, acompound Ma1 (42.1 g) was added in several batches, then, the mixturewas stirred at −70° C. for 2 hours. Into this, methanol (40 mL) wasdropped over a period of 1 hour, then, the mixture was heated up to roomtemperature. Thereafter, the solvent was distilled off by concentratingunder reduced pressure, and toluene and water were added. Thereafter, anaqueous layer was separated and the resultant organic layer was washedwith water. The resultant organic layer was concentrated under reducedpressure, and the resultant residue was purified by using a silica gelcolumn (mobile phase: a mixed solvent of hexane and ethyl acetate),thereby obtaining 71 g of a compound Ma3 as a colorless oil.

This operation was repeated, thereby obtaining a necessary amount of thecompound Ma3.

¹H-NMR (CDCl₃, 300 MHz): δ (ppm): 2.43 (1H, s), 3.07-3.13 (4H, m), 6.95(1H, d), 7.07 (1H. s), 7.18-7.28 (3H, m), 7.28-7.40 (4H, m), 7.66 (2H,s).

A gas in a flask equipped with a stirrer was purged with a nitrogen gas,then, the compound Ma3 (72.3 g), toluene (723 mL) and triethylsilane(118.0 g) were added, and the mixture was heated up to 70° C. Into this,methanesulfonic acid (97.7 g) was dropped over a period of 1.5 hours,then, the mixture was stirred at 70° C. for 0.5 hours. Thereafter, themixture was cooled down to room temperature, and toluene (1 L) and water(1 L) were added, then, an aqueous layer was separated. The resultantorganic layer was washed with water, a 5 wt % sodium hydrogen carbonateaqueous solution and water in this order.

The resultant organic layer was concentrated under reduced pressure, andthe resultant coarse product was recrystallized from a mixed solvent oftoluene and ethanol, thereby obtaining 51.8 g of a compound Ma4 as awhite solid. This operation was repeated, thereby obtaining a necessaryamount of the compound Ma4.

¹H-NMR (CDCl₃, 300 MHz): δ (ppm): 3.03-3.14 (4H, m), 4.99 (1H, s), 6.68(1H, s), 6.92-7.01 (2H, m), 7.20-7.28 (2H, m), 7.29-7.38 (4H, m), 7.78(2H, d).

A gas in a flask equipped with a stirrer was purged with a nitrogen gas,then, a compound Mb1 (185.0 g), a compound Mb2 (121.1 g), copper iodide(I) (3.2 g), dichloromethane (185 mL) and triethylamine (2.59 L) wereadded, and the mixture was heated up to the reflux temperature.Thereafter, the mixture was stirred at the reflux temperature for 0.5hours, and cooled down to room temperature. To this was addeddichloromethane (1.85 L), then, the mixture was filtrated through afilter paved with celite. To the resultant filtrate was added a 10 wt %sodium hydrogen carbonate aqueous solution, then, an aqueous layer wasseparated. The organic layer was washed with water twice, washed with asaturated sodium chloride aqueous solution, then, magnesium sulfate wasadded. The resultant mixture was filtrated, and the resultant filtratewas concentrated under reduced pressure. The resultant residue waspurified by using a silica gel column (mobile phase: a mixed solvent ofchloroform and ethyl acetate), thereby obtaining a coarse product. Thisresultant coarse product was dissolved in ethanol (1.4 L), then,activated carbon (5 g) was added, and the mixture was filtrated. Theresultant filtrate was concentrated under reduced pressure, and theresultant residue was recrystallized from hexane, thereby obtaining 99.0g of a compound Mb3 as a white solid. This operation was repeated,thereby obtaining a necessary amount of the compound Mb3.

¹H-NMR (DMSO-de, 300 MHz): δ (ppm): 1.52-1.55 (8H, m), 2.42 (4H, t),3.38-3.44 (4H, m), 4.39-4.43 (2H, m), 7.31 (4H, s).

A gas in a flask equipped with a stirrer was purged with a nitrogen gas,then, the compound Mb3 (110.0 g), ethanol (1.65 L) and palladium/carbon(Palladium weight: 10%) (11.0 g) were added, and the mixture was heatedup to 30° C. Thereafter, a gas in the flask was purged with a hydrogengas. Thereafter, the mixture was stirred at 30° C. for 3 hours whilefeeding a hydrogen gas into the flask. Thereafter, a gas in the flaskwas purged with a nitrogen gas. The resultant mixture was filtrated, andthe resultant filtrate was concentrated under reduced pressure. Theresultant residue was purified by using a silica gel column (mobilephase: a mixed solvent of chloroform and ethyl acetate), therebyobtaining a coarse product. This resultant coarse product wasrecrystallized from hexane, thereby obtaining 93.4 g of a compound Mb4as a white solid.

¹H-NMR (CDCl₃, 300 MHz): δ (ppm): 1.30-1.40 (8H, m), 1.55-1.65 (8H, m),2.58 (4H, t), 3.64 (4H, t), 7.09 (4H, s).

¹³C-NMR (CDCl₃, 75 MHz): δ (ppm): 25.53, 28.99, 31.39, 32.62, 35.37,62.90, 128.18, 139.85.

A gas in a flask equipped with a stirrer was purged with a nitrogen gas,then, the compound Mb4 (61.0 g), pyridine (0.9 g) and toluene (732 mL)were added, and the mixture was heated up to 60° C. Into this, thionylchloride (91.4 g) was dropped over a period of 1.5 hours, then, themixture was stirred at 60° C. for 5 hours. The resultant mixture wascooled down to room temperature, then, concentrated under reducedpressure. The resultant residue was purified by using a silica gelcolumn (mobile phase: a mixed solvent of hexane and ethyl acetate),thereby obtaining 64.3 g of a compound Mb5 as a colorless oil.

¹H-NMR (CDCl₃, 300 MHz): δ (ppm): 1.35-1.40 (4H, m), 1.41-1.50 (4H, m),1.60-1.68 (4H, m), 1.75-1.82 (4H, m), 2.60 (4H, t), 3.55 (4H, t), 7.11(4H, s).

A gas in a flask equipped with a stirrer was purged with a nitrogen gas,then, the compound Mb5 (42.0 g), an iron powder (1.7 g), iodine (0.3 g)and dichloromethane (800 mL) were added. Thereafter, the whole flask waslight-shielded, and cooled at 0 to 5° C. Into this, a mixed solution ofbromine (44.7 g) and dichloromethane (200 mL) was dropped over a periodof 1 hour, then, the mixture was stirred at 0 to 5° C. overnight. Theresultant mixed solution was added to water (1.2 L) cooled at 0 to 5°C., then, an organic layer was separated. The organic layer was washedwith a 10 wt % sodium thiosulfate aqueous solution, and further, washedwith a saturated sodium chloride aqueous solution and water in thisorder. To the resultant organic layer was added sodium sulfate, then,the mixture was filtrated, and the resultant filtrate was concentratedunder reduced pressure. The resultant residue was purified by using asilica gel column (mobile phase: hexane), thereby obtaining a coarseproduct. This resultant coarse product was recrystallized from hexane,thereby obtaining 47.0 g of a compound Mb6 as a white solid.

¹H-NMR (CDCl₃, 300 MHz): δ (ppm): 1.38-1.45 (4H, m), 1.47-1.55 (4H, m),1.57-1.67 (4H, m), 1.77-1.84 (4H, m), 2.66 (4H, t), 3.55 (4H, t), 7.36(2H, s).

A gas in a flask equipped with a stirrer was purged with a nitrogen gas,then, sodium iodide (152.1 g) and acetone (600 mL) were added, and themixture was stirred at room temperature for 0.5 hours. To this thecompound Mb6 (40.0 g) was added, then, the mixture was heated up to thereflux temperature, and stirred at the reflux temperature for 24 hours.Thereafter, the mixture was cooled down to room temperature, and theresultant mixed solution was added to water (1.2 L). The deposited solidwas separated by filtration, then, washed with water, thereby obtaininga coarse product. This resultant coarse product was recrystallized froma mixed solution of toluene and methanol, thereby obtaining 46.0 g of acompound Mb7 as a white solid. This operation was repeated, therebyobtaining a necessary amount of the compound Mb7.

¹H-NMR (CDCl₃, 300 MHz): δ (ppm):1.35-1.50 (8H, m), 1.57-1.65 (4H, m),1.80-1.89 (4H, m), 2.65 (4H, t), 3.20 (4H, t), 7.36 (2H, s).

A gas in a flask equipped with a stirrer was purged with a nitrogen gas,then, sodium hydride (60 wt %, dispersed in liquid paraffin) (9.4 g),tetrahydrofuran (110 mL) and the compound Mb7 (63.2 g) were added. Tothis, a compound Ma4 (55.0 g) was added in several batches, then, themixture was stirred for 12 hours. To this were added toluene (440 mL)and water (220 mL), then, an aqueous layer was separated. The organiclayer was washed with water, then, magnesium sulfate was added. Theresultant mixed solution was filtrated, and the resultant filtrate wasconcentrated under reduced pressure, thereby obtaining a coarse product.This resultant coarse product was purified by using a silica gel column(mobile phase: a mixed solvent of hexane and toluene). Thereafter, theproduct was recrystallized from heptane, thereby obtaining 84.1 g of acompound Mb8 as a white solid.

¹H-NMR (CDCl₃, 300 MHz): δ (ppm): 0.70-0.76 (4H, m), 1.10-1.21 (8H, m),1.32-1.44 (4H, m), 2.39-2.58 (8H, m), 3.00-3.12 (8H, m), 6.82-6.94 (4H,m), 7.00-7.05 (2H, m), 7.17-7.28 (10H, m), 7.30-7.38 (4H, m), 7.71-7.77(4H, m).

A gas in a flask equipped with a stirrer was purged with a nitrogen gas,then, the compound Mb8 (84.0 g),[1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloridedichloromethane adduct (PdCl₂ (dppf).CH₂ Cl₂, 2.2 g),bis(pinacolato)diboron (68.3 g), potassium acetate (52.8 g) andcyclopentyl methyl ether (840 mL) were added, and the mixture was heatedup to the reflux temperature, then, stirred at the reflux temperaturefor 5 hours. Thereafter, the mixture was cooled down to roomtemperature, and toluene (500 mL) and water (300 mL) were added, then,an aqueous layer was separated. The organic layer was washed with water,then, activated carbon (18.5 g) was added. The resultant mixed solutionwas filtrated, and the resultant filtrate was concentrated under reducedpressure, thereby obtaining a coarse product. This coarse product waspurified by using a silica gel column (mobile phase: a mixed solvent ofhexane and toluene). Thereafter, an operation of recrystallization froma mixed solution of toluene and acetonitrile was repeated, therebyobtaining 45.8 g of a monomer 2 as a white solid.

¹H-NMR (CDCl₃, 300 MHz): δ (ppm): 0.70-0.76 (4H, m), 1.24-1.40 (36H, m),2.39-2.48 (4H, m), 2.66-2.75 (4H, m), 3.00-3.10 (8H, m), 6.76-6.90 (4H,m), 7.00-7.05 (2H, m), 7.19-7.30 (8H, m), 7.30-7.36 (4H, m), 7.43 (2H,s), 7.72 (4H, d).

<Synthesis Example 3> Synthesis of Monomer 3

Under a nitrogen gas atmosphere, a compound Me 1 (26 g, 39.6 mmol) wasdissolved in tetrahydrofuran (500 mL) and the solution was cooled to 0°C. to 5° C. Potassium tert-butoxide (17.75 g, 158.5 mmol) was addedslowly at a temperature in the range of 0° C. to 5° C., the reactionsolution was allowed to warm to room temperature and stirred for 24 h.Ice water (500 mL) was added to the reaction solution, and afterallowing to stand still, the separated organic layer was separated fromthe aqueous layer and combined with the ethyl acetate extract of theaqueous layer. The organic layer was concentrated under reduced pressureto remove the solvent, to give an oil. This oil was purified by silicagel column chromatography using hexane, to obtain 14.5 g of the intendedcompound Mc2.

¹H-NMR (400 MHz, CDCl₃): δ (ppm)=7.37 (s, 2H), 5.81-5.87 (m, 2H),4.96-5.07 (m, 4H), 2.67 (t, J=7.64 Hz, 4H), 2.09-2.15 (m, 4H), 1.57-1.64(m, 4H), 1.47-1.53 (m, 4H).

¹³C-NMR (100 MHz, CDCl₃): δ (ppm)=141.19, 138.67, 133.79, 123.08,114.60, 35.36, 33.54, 29.28, 28.56.

Under a nitrogen gas atmosphere, the compound Mc2 (11.66 g, 29.1 mmol)was dissolved in tetrahydrofuran (220 mL), the solution was cooled to−75° C., and sec-butyllithium (94 mL, 131.1 mmol) was dropped over aperiod of 2 hours at an internal temperature of −65° C. or lower, andthe mixture was stirred for 5.5 hours at an internal temperature of −65°C. or lower. Into the reaction solution, isopropyl pinacol borate (30mL, 145.7 mmol) was dropped over a period of 30 minutes at −70° C. Thereaction solution was warmed to room temperature and stirred overnight.Then, the reaction solution was cooled to 0° C., a 2 mol/L hydrochloricacid diethyl ether solution was dropped until the reaction solutionbecame transparent. The product was extracted with diethyl ether, andconcentrated under reduced pressure to remove the solvent, to give asolid. Acetonitrile (150 mL) was added to this solid, and the mixturewas stirred at room temperature for 2 hours, and the obtained solid wasfiltered. Acetonitrile (100 mL) was added again to this solid, followedby stirring at room temperature for 2 hours, and further,recrystallization with acetonitrile was performed twice, to obtain 3.60g of the intended monomer 3. The HPLC area percentage value of themonomer 3 was 99.90%. The filtrates of acetonitrile at the time ofrecrystallization were combined and recrystallization with acetonitrilewas performed twice, to obtain 1.4 g of a monomer 3.

1H-NMR (500 MHz, THF-d8): δ (ppm)=7.53 (s, 2H), 5.83 (m, 2H), 4.99 (d,2H), 4.90 (d, 2H), 2.82 (t, 4H), 2.07 (m, 4H), 1.56 (m, 4H), 1.45 (m,4H), 1.33 (s, 24H).

<Synthesis Example 4> Synthesis of Polymer Compound 1

An inert gas atmosphere was prepared in a reaction vessel, then, themonomer 1 (0.49334 g), the monomer 2 (0.12976 g), the monomer 3 (0.06195g), the monomer 4 (1.14646 g), dichlorobis(tris-o-methoxyphenylphosphine)palladium (2.20 mg) and toluene (30 mL)were added and heated at 105° C.

A 20 wt % tetraethylammonium hydroxide aqueous solution (8.3 mL) wasdropped thereto, and the mixture was refluxed for 6 hours. Thereafter,phenylboronic acid (61.0 mg) anddichlorobis(triphenylphosphine)palladium (1.1 mg) were added and themixture was refluxed for 14.5 hours. Thereafter, an aqueous sodiumdiethyldithiocarbamate solution was added thereto, and the mixture wasstirred at 80° C. for 2 hours. After cooling, the reaction solution waswashed with water twice, with a 3 wt % acetic acid aqueous solutiontwice and with water twice, and the resultant solution was dropped intomethanol, to cause generation of a precipitate. The obtained precipitatewas dissolved in toluene and purified by passing through an aluminacolumn and a silica gel column in this order. The resultant solution wasdropped into methanol, and the mixture was stirred, then, the resultantprecipitate was isolated by filtration and dried, to obtain 1.05 g of apolymer compound 1. The polystyrene-equivalent number-average molecularweight of the polymer compound 1 was 2.4×10⁴, and thepolystyrene-equivalent weight-average molecular weight thereof was1.8×10⁵.

The polymer compound 1 is a copolymer constituted of a constitutionalunit derived from the monomer 1, a constitutional unit derived from themonomer 2, a constitutional unit derived from the monomer 3 and aconstitutional unit derived from the monomer 4 at a molar ratio of40:5:5:50 according to the theoretical values calculated from theamounts of the charged raw materials.

<Synthesis Example 5> Synthesis of Metal Complex 1

Into a reaction vessel, 226 mg of iridium chloride, 760 mg of Ligand 1-1(synthesized according to the method described in JP-A No. 2013-147551),2 mL of water and 6 mL of 2-butoxyethanol were added, and a nitrogenatmosphere was prepared in the reaction vessel, then, the mixture wasrefluxed with heating for 17 hours. The resultant reaction mixture wasallowed to cool, then, water and dichloromethane were added, and theorganic layer was washed. The washed organic layer was concentrated anddried, to obtain 840 mg of M1-stage1. Into the reaction vessel, 840 mgof the resultant M1-stage1 and 1300 mg of Ligand 1-1 were added, and anargon gas atmosphere was prepared in the reaction vessel. Thereafter,165 mg of silver trifluorosulfonate and 1.25 mL of diethylene glycoldimethyl ester were added thereto, and the mixture was refluxed withheating for 15 hours. The resultant reaction mixture was allowed tocool, then, dichloromethane was added and the resultant suspension wasfiltered under suction. The resultant filtrate was separated by aseparatory funnel, and the resultant organic layer was concentrated. Theresultant concentrate was purified by silica gel column chromatography(a mixed solvent of dichloromethane and ethyl acetate), to give a yellowsolid. The resulting yellow solid was crystallized using a mixed solventof dichloromethane and methanol, then, crystallized using using a mixedsolvent of dichloromethane and hexane, to give 850 mg of a metal complex1 as a yellow powder.

The results of ¹H-NMR analysis are shown below.

¹H-NMR: δ (ppm)=7.82 (d, 3H), 7.75 (d, 6H), 7.72 (d, 3H), 7.62 (d, 12H),7.48 ((dd, 3H), 1.96 (ddd, 3H), 7.20 (dd, 3H), 6.87 (d, 3H), 4.27 (s,9H), 2.26-1.37 (s, 54H), 1.05 (m, 6H), 0.73 (t, 9H).

The LC analysis conditions are as follows.

The sample was diluted with toluene so that the metal complexconcentration was 0.2 wt % to 0.3 wt %, and analyzed.

Apparatus: LC-20A (manufactured by Shimaazu Corporation)

Column: SUMIPAX ODS Z-CLUE (ϕ 4.6×250 mm, 3 μm, manufactured by SumikaChemical Analysis Service, Ltd.)

Column temperature: 15° C.

Detector: photodiode array detector (SPD-M20A, manufactured by ShimadzuCorporation)

Detection wavelength: 254 nm

Mobile phase: solution A: acetonitrile, solution B: THF

Conditions for mobile phase: solution B 0%-40 minutes-solution B 50% (10minutes)-10 minutes-solution B 100%

Flow rate: 1.0 ml/min

Sample injection amount: 1 μL

The results of LC analysis are shown below.

When the LC purity was 99.7 9% and the content of the metal complex 1was taken as 100, the total amount of metal complexes having a molecularweight larger by 16 than that of the metal complex 1 was 0.12. Metalcomplexes having a molecular weight larger by 32 or 48 than that of themetal complex 1 were undetected.

LC-MS (APCI, positive) m/z: 1815.0 ([M+H]⁺)

<Synthesis Example 6> Synthesis of Metal Complex 2

<Synthesis of M2-Stage1>

Into a reaction vessel, 22.17 g of Ligand 2-1 (synthesized according tothe method described in JP-A No. 2011-105701), 6.95 g of iridiumchloride trihydrate, 96 mL of 2-ethoxyethanol and 32 mL of water wereadded, an argon gas flow was prepared in the reaction vessel, then, themixture was stirred at 140° C. for 15 hours. The resultant reactionmixture was allowed to cool, then, separated by filtration, and theresultant residue was washed with 150 mL of methanol, 100 mL of waterand 150 mL of methanol in this order, to obtain a red solid. Theresultant red solid was dissolved in 200 mL of chloroform, then, 300 mLof ethanol was added, and the mixture was refluxed for 2 hours. Theresultant reaction mixture was allowed to cool, then, separated byfiltration, and the resultant solid was washed with ethanol.Crystallization using a mixed solvent of chloroform and ethanol wasrepeated 3 times, then, the resultant solids were collected and driedunder reduced pressure, to obtain 20.03 g of M2-stage1.

<Synthesis of Metal Complex 2>

Into a reaction vessel, 759 mg of M2-stage1, 330 mg of Ligand 2-2(synthesized according to the method described in InternationalPublication WO 2006/062226), 9 mL of diglyme and 157 mg of silvertrifluoromethanesulfonate were added, an argon gas flow was prepared inthe reaction vessel, then, the mixture was stirred at 100° C. for 10hours. The resultant reaction mixture was allowed to cool, then, 50 mLof pure water was added, and the generated precipitate was separated byfiltration. To the resultant precipitate, 40 mL of a mixed solvent oftoluene and hexane (1/2 (volume ratio)) was added, then, the mixture wasfiltered. The resultant filtrate was dehydrated over sodium sulfate. Theresultant solution was filtered, and the resultant solid was purified bysilica gel column chromatography (a mixed solvent of hexane and toluene(1/1.5 (volume ratio))), then, the solvent was distilled off. Theresultant residue was washed with 50 mL of methanol and dried underreduced pressure, to give 252 mg of a metal complex 2.

The LC analysis conditions are the same as those of the metal complex 1.

The results of LC analysis are shown below.

When the LC purity was 98.02% and the content of the metal complex 2 wastaken as 100, the total amount of metal complexes having a molecularweight larger by 32 than that of the metal complex 2 was 0.12, and metalcomplexes having a molecular weight larger by 16 or 48 than that of themetal complex 2 were undetected.

LC-MS (APCI, positive) m/z: 1732.8 ([M+H]⁺)

<Synthesis Example 7> Synthesis of Metal Complex 3

<Synthesis of M3-Stage1>

Into a reaction vessel, 13.0 g of Ligand 3-1 (synthesized according tothe method described in International Publication WO 2008/111658), 4.12g of iridium(III) chloride trihydrate, 290 ml of ethoxyethanol and 116ml of water were added, then, the mixture was refluxed with heating for23 hours. The resultant reaction mixture was cooled down to roomtemperature, then, 2 90 ml of methanol was added and the mixture wasstirred at room temperature for 15 minutes, then, the deposited crystalwas filtrated. The resultant crystal was washed with methanol, water andhexane in this order, then, dried under reduced pressure at 30° C., toobtain 13.11 g of M3-stage1.

<Synthesis of Metal Complex 3>

A nitrogen gas atmosphere was prepared in a reaction vessel, then, 13.11g of M3-stage1, 13.48 g of Ligand 3-1, 2.77 g of silvertrifluoromethanesulfonate and 130 ml of ethylene glycol dimethyl etherwere added, and the mixture was stirred at 150° C. for 2 hours. Theresultant reaction mixture was cooled down to room temperature, then,1150 ml of methanol was added, and the mixture was stirred at roomtemperature for 30 minutes. The deposited crystal was filtrated, theresultant crystal was washed with methanol, then, dried under reducedpressure at 30° C., to obtain 15.60 g of a crude product. The resultantcrude product was purified by silica gel column chromatography (a mixedsolvent of toluene and hexane (2:1 (volume ratio))), to obtain 9.30 g ofa metal complex 3.

The results of ¹H-NMR analysis are shown below.

¹H-NMR: δ (ppm)=1.38 (s, 54H), δ 6.93 (dd, J=6.3, 6.6 Hz, 3H), δ 7.04(br, 3H), δ 7.30 (d, J=7.9 Hz, 3H), δ 7.48 (d, J=7.3 Hz, 12H), δ7.61-7.70 (m, 21H), δ 7.82 (s, 6H), δ 8.01 (s, 3H), δ 8.03 (d, J=7.9 Hz,3H)

The LC analysis conditions are as follows.

The sample was diluted with toluene so that the metal complexconcentration was 0.2 wt % to 0.3 wt %, and analyzed.

Apparatus: LC-20A (manufactured by Shimaazu Corporation)

Column: SUMIPAX ODS Z-CLUE (ϕ 4.6×250 mm, 3 μm, manufactured by SumikaChemical Analysis Service, Ltd.)

Column temperature: 15° C.

Detector: photodiode array detector (SPD-M20A, manufactured by ShimadzuCorporation)

Detection wavelength: 254 nm

Mobile phase: solution A: acetonitrile, solution B: THF

Conditions for mobile phase: solution B 10% (0 min)-50 min-solution B20% (0 min)-10 min-solution B 50% (0 min)-20 min-100% (0 min)

Flow rate: 1.0 ml/min

Sample injection amount: 1 μL

The results of LC analysis are shown below.

When the LC purity was 99.95% and the content of the metal complex 3 wastaken as 100, the total amount of metal complexes having a molecularweight larger by 16 than that of the metal complex 3 was 0.01, and metalcomplexes having a molecular weight larger by 32 or 48 than that of themetal complex 3 were undetected.

LC-MS (APCI, positive) m/z: 1676.7 ([M+H]⁺)

<Example 1> Fabrication and Evaluation of Light Emitting Device 1

An ITO film having a thickness of 45 nm was attached to a glasssubstrate by a sputtering method, to form an anode. On the anode, apolythiophene-sulfonic acid type hole injecting agent (AQ-1200,manufactured by Flextronics Co., Ltd.) was spin-coated to form a filmwith a thickness of 35 nm, and the film was heated on a hot plate at170° C. for 15 minutes under an air atmosphere, to form a hole injectionlayer.

The polymer compound 1 was dissolved in xylene at a concentration of0.7% by weight. The resultant xylene solution was spin-coated on thehole injection layer to form a film with a thickness of 20 nm, and thefilm was heated on a hot plate at 180° C. for 60 minutes under anitrogen gas atmosphere, to form a hole transporting layer.

A host compound 1 (manufactured by Luminescense Technology) and themetal complex 1 (host compound 1/metal complex 1=70 wt %/30 wt %) weredissolved in toluene at a concentration of 2.0% by weight. The resultanttoluene solution (hereinafter, referred to as “toluene solution A”) wasstored in a glove box purged with a nitrogen gas for 2 weeks under lightshielding at ambient temperature. Thereafter, the stored toluenesolution was spin-coated on the hole transporting layer to form a filmwith a thickness of 80 nm, and the film was heated at 130° C. for 10minutes under a nitrogen gas atmosphere, to form a light emitting layer.

In the LC analysis immediately before formation of the light emittinglayer (film), when the content of the metal complex 1 in the toluenesolution A was taken as 100, the total amount of metal complexes havinga molecular weight larger by 16 than that of the metal complex 1 was0.02, and metal complexes having a molecular weight larger by 32 or 48than that of the metal complex 1 were undetected.

A polymer compound 2 synthesized according to the synthesis methoddescribed in International Publication WO 2010/117075 was dissolved in2,2,3,3,4,4,5,5-octafluoro-1-pentanol at a concentration of 0.25% byweight. The resultant solution was spin-coated on the light emittinglayer to form a film with a thickness of 10 nm, and the film was heatedat 130° C. for 10 minutes under a nitrogen gas atmosphere, to form anelectron transporting layer.

The substrate carrying thereon the light emitting layer formed wasplaced in a vapor deposition machine and the inner pressure was reducedto 1.0×10⁻⁴ Pa or less, then, as a cathode, sodium fluoride wasvapor-deposited with a thickness of about 4 nm on the light emittinglayer, then, aluminum was vapor-deposited with a thickness of about 80nm on this. After vapor deposition, sealing with a glass substrate wasperformed, to fabricate a light emitting device 1.

When voltage was applied to the light emitting device 1, EL emission wasobserved. The results are shown in Table 2.

<Example 2> Fabrication and Evaluation of Light Emitting Device

A light emitting device 2 was fabricated in the same manner as inExample 1, except that the storage period of the toluene solution A waschanged from 2 weeks to 4 weeks in Example 1.

In the LC analysis immediately before formation of the light emittinglayer (film), when the content of the metal complex 1 in the toluenesolution A was taken as 100, the total amount of metal complexes havinga molecular weight larger by 16 than that of the metal complex 1 was0.02, and metal complexes having a molecular weight larger by 32 or 48than that of the metal complex 1 were undetected.

When voltage was applied to the light emitting device 2, EL emission wasobserved. The results are shown in Table 2.

<Comparative Example 1> Fabrication and Evaluation of Light EmittingDevice C1

A light emitting device C1 was fabricated in the same manner as inExample 1, except that the toluene solution A was not stored in Example1.

In the LC analysis immediately before formation of the light emittinglayer (film), when the content of the metal complex 1 in the toluenesolution A was taken as 100, the total amount of metal complexes havinga molecular weight larger by 16 than that of the metal complex 1 was0.02, and metal complexes having a molecular weight larger by 32 or 48than that of the metal complex 1 were undetected.

A light emitting device C1 was fabricated in the same manner as inExample 1, except that the toluene solution A was used without storagein Example 1.

When voltage was applied to the light emitting device C1, EL emissionwas observed. The results are shown in Table 2.

<Comparative Example 2> Fabrication and Evaluation of Light EmittingDevice C2

A light emitting device C2 was fabricated in the same manner as inExample 1, except that the toluene solution A was stored in a glove boxpurged with a nitrogen gas for 1 week under fluorescent illumination atambient temperature instead of storage of the toluene solution A in aglove box purged with a nitrogen gas for 2 weeks under light shieldingin Example 1.

In the LC analysis immediately before formation of the light emittinglayer (film), when the content of the metal complex 1 in the toluenesolution A was taken as 100, the total amount of metal complexes havinga molecular weight larger by 16 than that of the metal complex 1 was0.49, and metal complexes having a molecular weight larger by 32 or 48than that of the metal complex 1 were undetected.

When voltage was applied to the light emitting device C2, EL emissionwas observed. The results are shown in Table 2.

<Comparative Example 3> Fabrication and Evaluation of Light EmittingDevice C3

A light emitting device C3 was fabricated in the same manner as inExample 1, except that the toluene solution A was stored in a glove boxpurged with a nitrogen gas for 4 weeks under fluorescent illumination atambient temperature instead of storage of the toluene solution A in aglove box purged with a nitrogen gas for 2 weeks under light shieldingin Example 1.

In the LC analysis immediately before formation of the light emittinglayer (film), when the content of the metal complex 1 in the toluenesolution A was taken as 100, the total amount of metal complexes havinga molecular weight larger by 16 than that of the metal complex 1 was0.71, and metal complexes having a molecular weight larger by 32 or 48than that of the metal complex 1 were undetected.

When voltage was applied to the light emitting device C3, EL emissionwas observed. The results are shown in Table 2.

The evaluation results are shown in Table 2. The relative value of theexternal quantum efficiency (maximum value) of each light emittingdevice is shown when the external quantum efficiency (maximum value) ofthe light emitting device C1 is taken as 1.00.

TABLE 2 the total amount of metal complexes having a molecular weightlarger by 16 value value external than that of a metal of of quantumlight ink complex of which for- for- efficiency emitting storage contentis taken mula mula (relative device condition as 100 (1) (2) value) 1light 0.02 1 0.0002 1.08 shielded for 2 weeks/under nitrogen gasatmosphere 2 light 0.02 1 0.0002 1.14 shielded for 4 weeks/undernitrogen gas atmosphere C1 no storage 0.02 — — 1.00 C2 irradiated 0.4925 0.0049 1.01 for 1 week/under nitrogen gas atmosphere C3 irradiated0.71 36 0.0071 0.48 for 4 weeks/under nitrogen gas atmosphere

<Example 3> Fabrication and Evaluation of Light Emitting Device 3

An ITO film having a thickness of 45 nm was attached to a glasssubstrate by a sputtering method, to form an anode. On the anode, apolythiophene-sulfonic acid type hole injecting agent (AQ-1200,manufactured by Flextronics Co., Ltd.) was spin-coated to form a filmwith a thickness of 35 nm, and the film was heated on a hot plate at170° C. for 15 minutes under an air atmosphere, to form a hole injectionlayer.

The polymer compound 1 was dissolved in xylene at a concentration of0.7% by weight. The resultant xylene solution was spin-coated on thehole injection layer to form a film with a thickness of 20 nm, and thefilm was heated on a hot plate at 180° C. for 60 minutes under anitrogen gas atmosphere, to form a hole transporting layer.

A host compound 2 synthesized according to the synthesis methoddescribed in JP-A No. 2015-110751 and the metal complex 2 (host compound2/metal complex 2=90 wt %/10 wt %) were dissolved in toluene at aconcentration of 2.2% by weight. The resultant toluene solution(hereinafter, referred to as “toluene solution B”) was stored in a glovebox purged with a nitrogen gas for 1 week under light shielding atambient temperature. Thereafter, the stored toluene solution wasspin-coated on the hole transporting layer to form a film with athickness of 80 nm, and the film was heated at 130° C. for 10 minutesunder a nitrogen gas atmosphere, to form a light emitting layer.

In the LC analysis immediately before formation of the light emittinglayer (film), when the content of the metal complex 2 in the toluenesolution B was taken as 100, the total amount of metal complexes havinga molecular weight larger by 32 than that of the metal complex 2 was0.10, and metal complexes having a molecular weight larger by 16 or 48than that of the metal complex 2 were undetected.

The substrate carrying thereon the light emitting layer formed wasplaced in a vapor deposition machine and the inner pressure was reducedto 1.0×10⁻⁴ Pa or less, then, as a cathode, sodium fluoride wasvapor-deposited with a thickness of about 4 nm on the light emittinglayer, then, aluminum was vapor-deposited with a thickness of about 80nm on this. After vapor deposition, sealing with a glass substrate wasperformed, to fabricate a light emitting device 3.

When voltage was applied to the light emitting device 3, EL emission wasobserved. The results are shown in Table 3.

<Example 4> Fabrication and Evaluation of Light Emitting Device 4

A light emitting device 4 was fabricated in the same manner as inExample 3, except that the storage period of the toluene solution B waschanged from 1 week to 2 weeks in Example 3.

In the LC analysis immediately before formation of the light emittinglayer (film), when the content of the metal complex 2 in the toluenesolution B was taken as 100, the total amount of metal complexes havinga molecular weight larger by 32 than that of the metal complex 2 was0.10, and metal complexes having a molecular weight larger by 16 or 48than that of the metal complex 2 were undetected.

When voltage was applied to the light emitting device 4, EL emission wasobserved. The results are shown in Table 3.

<Comparative Example 4> Fabrication and Evaluation of Light EmittingDevice C4

A light emitting device C4 was fabricated in the same manner as inExample 3, except that the toluene solution B was not stored in Example3.

In the LC analysis immediately before formation of the light emittinglayer (film), when the content of the metal complex 2 in the toluenesolution B was taken as 100, the total amount of metal complexes havinga molecular weight larger by 32 than that of the metal complex 2 was0.12, and metal complexes having a molecular weight larger by 16 or 48than that of the metal complex 2 were undetected.

When voltage was applied to the light emitting device C4, EL emissionwas observed. The results are shown in Table 3.

<Comparative Example 5> Fabrication and Evaluation of Light EmittingDevice C5

A light emitting device C5 was fabricated in the same manner as inExample 3, except that the toluene solution B was stored in a glove boxpurged with a nitrogen gas for 1 week under fluorescent illumination atambient temperature instead of storage of the toluene solution B in aglove box purged with a nitrogen gas for 1 week under light shielding atambient temperature in Example 3.

In the LC analysis immediately before formation of the light emittinglayer (film), when the content of the metal complex 2 in the toluenesolution B was taken as 100, the total amount of metal complexes havinga molecular weight larger by 32 than that of the metal complex 2 was0.78, and metal complexes having a molecular weight larger by 16 or 48than that of the metal complex 2 were undetected.

When voltage was applied to the light emitting device C5, EL emissionwas observed. The results are shown in Table 3.

<Comparative Example 6> Fabrication and Evaluation of Light EmittingDevice C6

A light emitting device C6 was fabricated in the same manner as inExample 3, except that the toluene solution B was stored in a glove boxpurged with a nitrogen gas for 2 weeks under fluorescent illumination atambient temperature instead of storage of the toluene solution B in aglove box purged with a nitrogen gas for 1 week under light shielding atambient temperature in Example 3.

In the LC analysis immediately before formation of the light emittinglayer (film), when the content of the metal complex 2 in the toluenesolution B was taken as 100, the total amount of metal complexes havinga molecular weight larger by 32 than that of the metal complex 2 was3.48, and metal complexes having a molecular weight larger by 16 or 48than that of the metal complex 2 were undetected.

When voltage was applied to the light emitting device C6, EL emissionwas observed. The results are shown in Table 3.

The evaluation results are shown in Table 3. The relative value of theexternal quantum efficiency (maximum value) of each light emittingdevice is shown when the external quantum efficiency (maximum value) ofthe light emitting device C4 is taken as 1.00.

TABLE 3 the total amount of metal complexes having a molecular weightlarger by 32 value value external than that of a metal of of quantumlight ink complex of which for- for- efficiency emitting storage contentis taken mula mula (relative device condition as 100 (1) (2) value) 3light 0.10 0.8 0.0010 1.11 shielded for 1 week/under nitrogen gasatmosphere 4 light 0.10 0.8 0.0010 1.09 shielded for 2 weeks/undernitrogen gas atmosphere C4 no storage 0.12 — — 1.00 C5 irradiated 0.78 70.0078 0.85 for 1 week/under nitrogen gas atmosphere C6 irradiated 3.4829 0.0348 0.41 for 2 weeks/under nitrogen gas atmosphere

<Example 5> Fabrication and Evaluation of Light Emitting Device 5

An ITO film having a thickness of 45 nm was attached to a glasssubstrate by a sputtering method, to form an anode. On the anode, apolythiophene-sulfonic acid type hole injecting agent (AQ-1200,manufactured by Flextronics Co., Ltd.) was spin-coated to form a filmwith a thickness of 35 nm, and the film was heated on a hot plate at170° C. for 15 minutes under an air atmosphere, to form a hole injectionlayer.

The polymer compound 1 was dissolved in xylene at a concentration of0.7% by weight. The resultant xylene solution was spin-coated on thehole injection layer to form a film with a thickness of 20 nm, and thefilm was heated on a hot plate at 180° C. for 60 minutes under anitrogen gas atmosphere, to form a hole transporting layer.

The host compound 1 and the metal complex 2 (host compound 1/metalcomplex 2=92.5 wt %/7.5 wt %) were dissolved in toluene at aconcentration of 2.0% by weight. The resultant toluene solution(hereinafter, referred to as “toluene solution C”) was stored for 2weeks under light shielding at ambient temperature in an air atmosphere.Thereafter, the stored toluene solution was spin-coated on the holetransporting layer to form a film with a thickness of 80 nm, and thefilm was heated at 130° C. for 10 minutes under a nitrogen gasatmosphere, to form a light emitting layer.

In the LC analysis immediately before formation of the light emittinglayer (film), when the content of the metal complex 2 in the toluenesolution C was taken as 100, the total amount of metal complexes havinga molecular weight larger by 32 than that of the metal complex 2 was0.33, and metal complexes having a molecular weight larger by 16 or 48than that of the metal complex 2 were undetected.

The substrate carrying thereon the light emitting layer formed wasplaced in a vapor deposition machine and the inner pressure was reducedto 1.0×10⁻⁴ Pa or less, then, as a cathode, sodium fluoride wasvapor-deposited with a thickness of about 4 nm on the light emittinglayer, then, aluminum was vapor-deposited with a thickness of about 80nm on the sodium fluoride layer. After vapor deposition, sealing with aglass substrate was performed, to fabricate a light emitting device 5.

When voltage was applied to the light emitting device 5, EL emission wasobserved. The results are shown in Table 4.

<Example 6> Fabrication and Evaluation of Light Emitting Device 6

A light emitting device 6 was fabricated in the same manner as inExample 5, except that the toluene solution C was stored for 5 hoursunder fluorescent illumination at ambient temperature in an airatmosphere, then, stored for 2 weeks under light shielding in an airatmosphere instead of storage of the toluene solution C for 2 weeksunder light shielding at ambient temperature in an air atmosphere.

In the LC analysis immediately before formation of the light emittinglayer (film), when the content of the metal complex 2 in the toluenesolution C was taken as 100, the total amount of metal complexes havinga molecular weight larger by 32 than that of the metal complex 2 was0.51, and metal complexes having a molecular weight larger by 16 or 48than that of the metal complex 2 were undetected.

When voltage was applied to the light emitting device 6, EL emission wasobserved. The results are shown in Table 4.

<Comparative Example 7> Fabrication and Evaluation of Light EmittingDevice C7

A light emitting device C7 was fabricated in the same manner as inExample 5, except that the toluene solution C was not stored in Example5.

In the LC analysis immediately before formation of the light emittinglayer (film), when the content of the metal complex 2 in the toluenesolution C was taken as 100, the total amount of metal complexes havinga molecular weight larger by 32 than that of the metal complex 2 was0.11, and metal complexes having a molecular weight larger by 16 or 48than that of the metal complex 2 were undetected.

When voltage was applied to the light emitting device C7, EL emissionwas observed. The results are shown in Table 4.

<Comparative Example 8> Fabrication and Evaluation of Light EmittingDevice C8

A light emitting device C8 was fabricated in the same manner as inExample 5, except that the toluene solution C was stored for 10 hoursunder fluorescent illumination at ambient temperature in an airatmosphere, then, stored for 2 weeks under light shielding in an airatmosphere instead of storage of the toluene solution C for 2 weeksunder light shielding at ambient temperature in an air atmosphere.

In the LC analysis immediately before formation of the light emittinglayer (film), when the content of the metal complex 2 in the toluenesolution C was taken as 100, the total amount of metal complexes havinga molecular weight larger by 32 than that of the metal complex 2 was0.87, and metal complexes having a molecular weight larger by 16 or 48than that of the metal complex 2 were undetected.

When voltage was applied to the light emitting device C8, EL emissionwas observed. The results are shown in Table 4.

The evaluation results are shown in Table 4. The relative value of theexternal quantum efficiency (maximum value) of each light emittingdevice is shown when the external quantum efficiency (maximum value) ofthe light emitting device C7 is taken as 1.00.

TABLE 4 the total amount of metal complexes having a molecular weightlarger by 32 value value external than that of a metal of of quantumlight ink complex of which for- for- efficiency emitting storage contentis taken mula mula (relative device condition as 100 (1) (2) value) 5light 0.33 3 0.0033 1.07 shielded for 2 weeks/under air atmosphere 6irradiated 0.51 5 0.0051 1.06 for 5 hours, light shielded for 2weeks/under air atmosphere C7 no storage 0.11 — — 1.00 C8 irradiated0.87 8 0.0087 0.80 for 10 hours, light shielded for 2 weeks/under airatmosphere

<Example 7> Fabrication and Evaluation of Light Emitting Device 7

An ITO film having a thickness of 45 nm was attached to a glasssubstrate by a sputtering method, to form an anode. On the anode, apolythiophene-sulfonic acid type hole injecting agent (AQ-1200,manufactured by Flextronics Co., Ltd.) was spin-coated to form a filmwith a thickness of 35 nm, and the film was heated on a hot plate at170° C. for 15 minutes under an air atmosphere, to form a hole injectionlayer.

The polymer compound 1 was dissolved in xylene at a concentration of0.7% by weight. The resultant xylene solution was spin-coated on thehole injection layer to form a film with a thickness of 20 nm, and thefilm was heated on a hot plate at 180° C. for 60 minutes under anitrogen gas atmosphere, to form a hole transporting layer.

The host compound 2 and the metal complex 3 (host compound 2/metalcomplex 3=70 wt %/30 wt %) were dissolved in toluene at a concentrationof 2.5% by weight. The resultant toluene solution (hereinafter, referredto as “toluene solution D”) was stored in a glove box purged with anitrogen gas for 1 week under light shielding at ambient temperature.Thereafter, the stored toluene solution was spin-coated on the holetransporting layer to form a film with a thickness of 80 nm, and thefilm was heated at 130° C. for 10 minutes under a nitrogen gasatmosphere, to form a light emitting layer.

In the LC analysis immediately before formation of the light emittinglayer (film), when the content of the metal complex 3 in the toluenesolution D was taken as 100, the total amount of metal complexes havinga molecular weight larger by 16 than that of the metal complex 3 was0.02, and metal complexes having a molecular weight larger by 32 or 48than that of the metal complex 3 were undetected.

The substrate carrying thereon the light emitting layer formed wasplaced in a vapor deposition machine and the inner pressure was reducedto 1.0×10⁻⁴ Pa or less, then, as a cathode, sodium fluoride wasvapor-deposited with a thickness of about 4 nm on the light emittinglayer, then, aluminum was vapor-deposited with a thickness of about 80nm on the sodium fluoride layer. After vapor deposition, sealing with aglass substrate was performed, to fabricate a light emitting device 7.

When voltage was applied to the light emitting device 7, EL emission wasobserved. The results are shown in Table 5.

<Example 8> Fabrication and Evaluation of Light Emitting Device

A light emitting device 8 was fabricated in the same manner as inExample 7, except that the storage period of the toluene solution D waschanged from 1 week to 2 weeks in Example 7.

In the LC analysis immediately before formation of the light emittinglayer (film), when the content of the metal complex 3 in the toluenesolution B was taken as 100, the total amount of metal complexes havinga molecular weight larger by 16 than that of the metal complex 3 was0.01, and metal complexes having a molecular weight larger by 32 or 48than that of the metal complex 3 were undetected.

When voltage was applied to the light emitting device 8, EL emission wasobserved. The results are shown in Table 5.

<Comparative Example 9> Fabrication and Evaluation of Light EmittingDevice C9

A light emitting device C9 was fabricated in the same manner as inExample 7, except that the toluene solution D was not stored in Example7.

In the LC analysis immediately before formation of the light emittinglayer (film), when the content of the metal complex 3 in the toluenesolution C was taken as 100, the total amount of metal complexes havinga molecular weight larger by 16 than that of the metal complex 3 was0.02, and metal complexes having a molecular weight larger by 32 or 48than that of the metal complex 3 were undetected.

When voltage was applied to the light emitting device C9, EL emissionwas observed. The results are shown in Table 5.

TABLE 5 the total amount of metal complexes having a molecular weightlarger by 16 value value external than that of a metal of of quantumlight ink complex of which for- for- efficiency emitting storage contentis taken mula mula (relative device condition as 100 (1) (2) value) 7light 0.02 1 0.0002 1.06 shielded for 1 week/under nitrogen gasatmosphere 8 light 0.01 0.5 0.0001 1.07 shielded for 2 weeks/undernitrogen gas atmosphere C9 no storage 0.02 — — 1.00

INDUSTRIAL APPLICABILITY

According to the film production method or the like of the presentinvention, a film excellent in the external quantum efficiency when usedfor a light emitting layer of a light emitting device is obtained.

1-15. (canceled)
 16. A film production method comprising an inkpreparation step of preparing an ink comprising a metal complexrepresented by the formula (1-B), a compound represented by the formula(H-2), and an organic solvent, an ink storage step of storing the inkprepared in the ink preparation step for 3 days or more under lightshielding, and a film formation step of forming a film by an applicationmethod using the ink stored in the ink storage step and in which thetotal content of metal complexes having a molecular weight larger by 16,32 or 48 than that of the metal complex represented by the formula (1-B)according to the area percentage value determined by liquidchromatography is 0.6 or less when the content of the metal complexrepresented by the formula (1-B) according to the area percentage valuedetermined by liquid chromatography is taken as 100:

wherein M represents an iridium atom or a platinum atom, n¹ representsan integer of 1 or more, n² represents an integer of 0 or more, andn¹+n² is 2 or 3, and n¹+n² is 3 when M is an iridium atom, while n¹+n²is 2 when M is a platinum atom, E^(11B), E^(12B), E^(13B), E^(14B),E^(21B), E^(22B), E^(23B) and E^(24B) each independently represent anitrogen atom or a carbon atom, and when a plurality of E^(11B),E^(12B), E^(13B), E^(14B), E^(21B), E^(22B), E^(23B) and E^(24B) arepresent, they may be the same or different at each occurrence, and whenE^(11B) is a nitrogen atom, R^(11B) is not present, when E^(12B) is anitrogen atom, R^(12B) is not present, when E^(13B) is a nitrogen atom,R^(13B) is not present, when E^(14B) is a nitrogen atom, R^(14B) is notpresent, when E^(21B) is a nitrogen atom, R^(21B) is not present, whenE^(22B) is a nitrogen atom, R^(22B) is not present, when E^(23B) is anitrogen atom, R^(23B) is not present, and when E^(24B) is a nitrogenatom, R^(24B) is not present, R^(11B), R^(12B), R^(13B), R^(14B),R^(21B), R^(22B), R^(23B) and R^(24B) each independently represent ahydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, acycloalkoxy group, an aryl group, an aryloxy group, a monovalentheterocyclic group, a halogen atom or a substituted amino group, orR^(11B) and R^(12B), R^(12B) and R^(13B), R^(13B) and R^(14B), R^(11B)and R^(21B), R^(21B) and R^(22B), R^(22B) and R^(23B), and R^(23B) andR^(24B) each are combined together to form an aromatic ring togetherwith the atoms to which they are attached, and the group represented byR^(11B), R^(12B), R^(13B), R^(14B), R^(21B), R^(22B), R^(23B) or R^(24B)optionally has a substituent, and when a plurality of R^(11B), R^(12B),R^(13B), R^(14B), R^(21B), R^(22B), R^(23B) and R^(24B) are present,they may be the same or different at each occurrence, and R^(11B) andR^(12B), R^(12B) and R^(13B), R^(13B) and R^(14B), R^(11B) and R^(21B),R^(21B) and R^(22B), R^(22B) and R^(23B), and R^(23B) and R^(24B) eachmay be combined together to form a ring together with the atoms to whichthey are attached, the ring R^(1B) represents a pyridine ring or adiazine ring constituted of a nitrogen atom, a carbon atom, E^(11B),E^(12B), E^(13B) and E^(14B), the ring R^(2B) represents a benzene ring,a pyridine ring or a diazine ring constituted of two carbon atoms,E^(21B), E^(22B), E^(23B) and E^(24B), and A¹-G¹-A² represents ananionic bidentate ligand, A¹ and A² each independently represent acarbon atom, an oxygen atom or a nitrogen atom, and these atoms each maybe an atom constituting a ring, G¹ represents a single bond or an atomicgroup constituting the bidentate ligand together with A¹ and A², andwhen a plurality of A¹-G¹-A² are present, they may be the same ordifferent:

wherein, Ar^(H1) and Ar^(H2) each independently represent an aryl groupor a monovalent heterocyclic group, and these groups each optionallyhave a substituent, n^(H3) represents an integer of 1, and L^(H1)represents a group represented by the formula (AA-4) or the formula(AA-14), and these groups each optionally have a substituent:

wherein, R represents a hydrogen atom, an alkyl group, a cycloalkylgroup, an aryl group or a monovalent heterocyclic group, and theplurality of R each may be the same or different.
 17. The filmproduction method according to claim 16, wherein the ink storage step isperformed under the condition of 0° C. to 50° C.
 18. The film productionmethod according to claim 16, wherein the ink storage step is performedunder an inert gas atmosphere.
 19. The film production method accordingto claim 16, wherein the metal complex (1-B) is a metal complexrepresented by the formula (1-B1), a metal complex represented by theformula (1-B2) or a metal complex represented by the formula (1-B3):

wherein M, n¹, n², R^(11b), R^(12B), R^(13B), R^(14B), R^(21B), R^(22B),R^(23B), R^(24B) and A¹-G¹-A² represent the same meaning as describedabove, and R^(15B), R^(16B), R^(17B) and R^(18B) each independentlyrepresent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxygroup, a cycloalkoxy group, an aryl group, an aryloxy group, amonovalent heterocyclic group, a halogen atom or a substituted aminogroup and these groups each optionally have a substituent, and when aplurality of R^(15B), R^(16B), R^(17B) and R^(18B) are present, they maybe the same or different at each occurrence.
 20. An ink storage methodcomprising an ink preparation step of preparing an ink comprising ametal complex represented by the formula (1-B), a compound representedby the formula (H-2), and an organic solvent, and a storage step ofstoring the ink prepared in the ink preparation step for 3 days or more,wherein the content of the metal complex represented by the formula(1-B) in the ink immediately after preparation of the ink preparationstep is defined as Cb[M], the total content of metal complexes having amolecular weight larger by 16, 32 or 48 than that of the metal complexrepresented by the formula (1-B) in the ink immediately after thepreparation is defined as Cb[M+16n], the content of the metal complexrepresented by the formula (1-B) in the ink immediately after storage ofthe storage step is defined as Ca[M], and the total content of metalcomplexes having a molecular weight larger by 16, 32 or 48 than that ofthe metal complex represented by the formula (1-B) in the inkimmediately after the storage is defined as Ca[M+16n], satisfying theformulae (1) and (2):0.1≤(Ca[M+16n]/Ca[M])/(Cb[M+16n]/Cb[M])≤20  (1)0<Ca[M+16n]/Ca[M]≤0.006  (2):

wherein M represents an iridium atom or a platinum atom, n¹ representsan integer of 1 or more, n² represents an integer of 0 or more, andn¹+n² is 2 or 3, and n¹+n² is 3 when M is an iridium atom, while n¹+n²is 2 when M is a platinum atom, E^(11B), E^(12B), E^(13B), E^(14B),E^(21B), E^(22B), E^(23B) and E^(24B) each independently represent anitrogen atom or a carbon atom, and when a plurality of E^(11B),E^(12B), E^(13B), E^(14B), E^(21B), E^(22B), E^(23B) and E^(24B) arepresent, they may be the same or different at each occurrence, and whenE^(11B) is a nitrogen atom, R^(11B) is not present, when E^(12B) is anitrogen atom, R^(12B) is not present, when E^(13B) is a nitrogen atom,R^(13B) is not present, when E^(14B) is a nitrogen atom, R^(14B) is notpresent, when E^(21B) is a nitrogen atom, R^(21B) is not present, whenE^(22B) is a nitrogen atom, R^(22B) is not present, when E^(23B) is anitrogen atom, R^(23B) is not present, and when E^(24B) is a nitrogenatom, R^(24B) is not present, R^(11B), R^(12B), R^(13B), R^(14B),R^(21B), R^(22B), R^(23B) and R^(24B) each independently represent ahydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, acycloalkoxy group, an aryl group, an aryloxy group, a monovalentheterocyclic group, a halogen atom or a substituted amino group, orR^(11B) and R^(12B), R^(12B) and R^(13B), R^(13B) and R^(14B), R^(11B)and R^(21B), R^(21B) and R^(22B), R^(22B) and R^(23B), and R^(23B) andR^(24B) each are combined together to form an aromatic ring togetherwith the atoms to which they are attached, and the group represented byR^(11B), R^(12B), R^(13B), R^(14B), R^(21B), R^(22B), R^(23B) or R^(24B)optionally has a substituent, and when a plurality of R^(11B), R^(12B),R^(13B), R^(14B), R^(21B), R^(22B), R^(23B) and R^(24B) are present,they may be the same or different at each occurrence, and R^(11B) andR^(12B), R^(12B) and R^(13B), R^(13B) and R^(14B), R^(11B) and R^(21B),R^(21B) and R^(22B), R^(22B) and R^(23B), and R^(23B) and R^(24B) eachmay be combined together to form a ring together with the atoms to whichthey are attached, the ring R^(1B) represents a pyridine ring or adiazine ring constituted of a nitrogen atom, a carbon atom, E^(11B),E^(12B), E^(13B) and E^(14B), the ring R^(2B) represents a benzene ring,a pyridine ring or a diazine ring constituted of two carbon atoms,E^(21B), E^(22B), E^(23B) and E^(24B), and A¹-G¹-A² represents ananionic bidentate ligand, A¹ and A² each independently represent acarbon atom, an oxygen atom or a nitrogen atom, and these atoms each maybe an atom constituting a ring, G¹ represents a single bond or an atomicgroup constituting the bidentate ligand together with A¹ and A², andwhen a plurality of A¹-G¹-A² are present, they may be the same ordifferent:

wherein, Ar^(H1) and Ar^(H2) each independently represent an aryl groupor a monovalent heterocyclic group, and these groups each optionallyhave a substituent, n^(H3) represents an integer of 1, and L^(H1)represents a group represented by the formula (AA-4) or the formula(AA-14), and these groups each optionally have a substituent:

wherein, R represents a hydrogen atom, an alkyl group, a cycloalkylgroup, an aryl group or a monovalent heterocyclic group, and theplurality of R each may be the same or different.
 21. The ink storagemethod according to claim 20, wherein the storage step is performedunder light shielding.
 22. The ink storage method according to claim 20,wherein the storage step is performed under the condition of 0° C. to50° C.
 23. The ink storage method according to claim 20, wherein thestorage step is performed under an inert gas atmosphere.
 24. The inkstorage method according to claim 20, wherein the metal complex (1-B) isa metal complex represented by the formula (1-B1), a metal complexrepresented by the formula (1-B2) or a metal complex represented by theformula (1-B3):

wherein M, n¹, n², R^(11B), R^(12B), R^(13B), R^(14B), R^(21B), R^(22B),R^(23B), R^(24B) and A¹-G¹-A² represent the same meaning as describedabove, and R^(15B), R^(16B), R^(17B) and R^(18B) each independentlyrepresent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxygroup, a cycloalkoxy group, an aryl group, an aryloxy group, amonovalent heterocyclic group, a halogen atom or a substituted aminogroup and these groups each optionally have a substituent, and when aplurality of R^(15B), R^(16B), R^(17B) and R^(18B) are present, they maybe the same or different at each occurrence.